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SGS MINERALS SERVICES TECHNICAL PAPER 2002-03 2002

A REVIEW OF THE BENEFICIATION AND EXTRACTIVE


METALLURGY OF THE PLATINUM GROUP ELEMENTS,
HIGHLIGHTING RECENT PROCESS INNOVATIONS
STEVE COLE, C. JOE FERRON SGS

INTRODUCTION

The six platinum-group elements (PGE): ruthenium, rhodium, palladium, osmium, iridium and platinum, together
with gold and silver, are considered to be precious metals. The recent spike in platinum and palladium prices
coupled with the projected increase in demand for the metals has fuelled a spate of exploration and new projects
in the PGE sector. Historically, primary producers of PGE metals have controlled the flow of information relating
to the mining and processing of these ores into the public domain. Very little published information relating to
individual operations and processes is available in comparison to the available literature relating to other metals.

The purpose of this paper is to provide authors have tried to briefly describe regarded platinum as an unwanted
a general overview of the issues commercial operations, as well as impurity in the silver that they were
relating to the processing of PGE ores. recent developments. In attempting to mining (Wagner, 1929).
Each topic discussed could easily be summarize a large body of work, much In the early 1900s, the only significant
the topic of a paper or book and so, in detail has been sacrificed. It is hoped uses for PGEs were for laboratory
many cases, only the surface of the that the information provided will be ware, as catalysts in the manufacturing
topic will be scratched. An attempt has sufficient to highlight some important process of sulphuric and nitric acids and
therefore been made to provide as many issues relating to the recovery of PGE in jewellery. The supply of this metal
references as possible. The intent of and to point the reader in the direction of was primarily from placer deposits in the
the authors is to review and compare more detailed information, should this be Russian Urals, southwestern Alaska and
metallurgical processes from a technical required. gold placers in California and from co-
point of view, without reference to the production of PGE metal from Sudbury
size of the operation. If one wants to TERMINOLOGY basin ores.
keep things in perspective, one should
not forget that in 2000, two countries, The terms PGE (Platinum Group In 1920, Hans Merensky discovered
namely South Africa and Russia, Elements) and PGM (Platinum Group the PGE reef bearing his name in the
produced more than 90% of the worlds Minerals) are often used interchangeably, Bushveld Igneous Complex in South
Pt, Pd and Rh supply (Appendix 1). and incorrectly, in the processing and Africa. For many years, this reef has
metallurgical literature. The terminology been the primary source for the majority
The paper is comprised of three main is confused further by PGM being of the PGE used worldwide.
sections. The first section briefly referred to as platinum group metals In the 1960s, improvements in analytical
describes the various PGE ore types and (which is strictly correct) but often leads techniques for determining trace
the mineralogical factors that affect the to the abbreviation of PGM, which refers amounts of PGE were developed. This
recovery of the PGEs. to the mineral and not the metal. The led to a better understanding of the
abbreviation, PM, should be avoided as geochemistry of PGE occurrences and
The second section deals with the this includes silver, and silver is not often hence an interest in looking for PGE
beneficiation of the PGE ores, describing associated with platinum group metals deposits in areas previously unexplored
the present status and discussing the (Cabri, 1981a). for PGE, such as the Stillwater area.
new trends.
HISTORY
Finally, the third section covers the
extractive metallurgy of the PGEs
Naturally occurring platinum and
(smelting and base metal refinery),
platinum-rich alloys have been known
again starting with reviewing the
to mankind for hundreds of years. The
existing operations and ending with
Spaniards named the native metal
a presentation of some of the new
platina or little silver, when they
trends and technologies in that area,
first encountered it in Colombia. They
and finally the PGE refining section, the
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 2

During the 1970s the United States classification presented in this paper from being fairly minor to being
government introduced legislation uses a combination of PGE content the deciding factor on project
mandating a reduction in the level of and mode of geological occurrence to economics.
pollutants emitted from automobile group ore types. Figure 1 depicts the Miscellaneous ores - These are ores
exhausts. Catalytic converters containing family tree of PGE ores as defined in which PGE values have been
platinum, palladium and rhodium (in by this classification. It should be noted noted but not recovered due to low
varied combinations) were accepted by that this classification system has been concentrations or recovered as a
the automobile industry as a technology largely adopted from the classification by-product with little or no economic
that would enable them to comply with presented in CIM Special Volume 23 advantage for the primary producer.
the new legislation. During the 1980s (Cabri, 1981a). The information presented Typically, little is known about the
and 1990s, the demand for platinum was in this section was largely assembled distribution and recovery of the PGE
growing every year in response to new from Chapters 10 (Naldrett, 1981) and 11 is these ores. An example of this type
requirements for catalysts in general (Cabri, 1981b) of that volume. of ore is that PGE is recovered from
(not only for the automobile industry), copper refining in the United States.
demands from the electronic industry, In this classification PGE ores are divided However, PGE content and recovery
and an increase in the amount of into three primary classes: is rarely determined for any of the
platinum used in the jewellery industry. PGE dominant - Those ores exploited concentrates feeding the smelting
Since the mid-1970s, the UG2 reef, primarily for their PGE content with process. PGE values in the primary ore
in the Bushveld Igneous Complex, other metals such at Cu, Ni and Co contribute no financial value.
has been increasingly exploited for its being produced as co-products. The
PGE content. Until recently, the mining economic values of the co-products A key point to note is that regardless of
companies exploiting this reef were the are, in general, minor in comparison to the mode of formation, a detailed study
same mining companies exploiting the the PGE values. of ore mineralogy is essential when
Merensky reef, some 15 to 330 meters Ni-Cu dominant ores - Those ores considering the metallurgical response of
above the UG2 reef. exploited primarily for the Ni and Cu a PGE ore since mineralogical variations
content. The PGE are produced as a within a particular mineralized horizon
In 1986, the Stillwater project heralded co-product. The economic importance (or reef) can be as significant as variation
the first major primary PGE project in of the PGE in these ores can vary between ore types. Cases in point are
North America. The Lac des Iles mine
(owned by North American Palladium
Ltd.) followed the Stillwater success
story in 1993. There are currently a
PGE Ores
number of exploration projects targeting
primary and secondary PGE deposits in
North America (see, for example, in this
volume: Farrow and Lightfoot; Barrie et PGE Dominant
Ni-Cu Dominant Miscellaneous
PGE Dominant Ores Ores
al.; Peek et al.)

Throughout the history of development


Porphyry Copper
Merensky Type Class I Ni-Cu Ore
of primary PGE deposits, Canada has Ores

supplied PGE metals as a by-product of


nickel and copper mining, primarily from
the Sudbury and Thompson regions. Inco Chromite Type Class II Ni-Cu Ore Copper-
Molybdenum Ores
started production of PGE in 1908 when
it opened a refinery in the U.K. to refine
ores from the Sudbury basin (Johnson
Placer Type Class III Ni-Cu Ore Carbonatite Ores
Matthey, 2001).

SECTION I: CLASSIFICATION Dunite Pipes Class IV Ni-Cu Ore Black Shales


OF PGE ORES AND
MINERALOGICAL FACTORS
RELATING TO RECOVERY Hydrothermal and
Other Ni-Cu Ores Supergene Cu
Ores
There are various methods
(mineralogical, sulphur content,
chromite content, grade of PGE,
Ni Laterites
etc.) used to classify ore types, each
with merits and disadvantages. The Figure 1. Classification of PGE Ores
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 3

the variations noted in the Merensky reef with most operations choosing a grind Great Dyke
on both a regional and mine site scale. size (P80) between 75 and 150 m. The The most recent publication on the Great
(Cawthorn et al., this volume). presence of talc in some areas can cause PGE deposits is that of Oberthur (this
significant process difficulties. volume). The BHP-owned mine, Hartley
PGE DOMINANT ORES Platinum, was exploiting this ore body
Merensky Type The Stillwater Complex and failed because of mining problems
These deposits occur in very large The production from the Stillwater relating to grade dilution (no marker for
bodies of basaltic magma, which complex originates from the J-M the reef such as the thin chromite layers
intruded into stable continental rocks. (Johns-Manville) reef. Unlike the associated with the Merensky reef).
In general, the Merensky type deposits Merensky reef where Pt is the primary The average head grades for this reef
are layered with disseminated sulphides. PGE, Pd is the most significant PGE are approximately 4 g/t PGE with about
The total sulphide content is fairly low; present in the Stillwater complex. 55% of the PGE content present as Pt.
in some cases, the PGE are associated The principal opaque minerals are The Mimosa mine has been exploiting
with chromite as well as sulphides. pentlandite, pyrrhotite and chalcopyrite. this ore body successfully for a number
Some examples of this type of deposit The principal PGE are braggite, of years and has just expanded its
are the Merensky Reef in South Africa vysotskite, moncheite and Pt-Fe alloys operations (Johnson Matthey, 2001).
(Cawthorn et al., this volume) and the (note the similarities with the Merensky
Great Dyke in Zimbabwe (Oberthur, PGE suite). It should be noted that Chromite Type
this volume). The Stillwater complex is there is a larger suite of opaque Two types of chromite deposits are
thought to be similar in nature to the minerals and PGE minerals associated economically or potentially economically
Merensky type deposit (Zientec et al., with the J-M reef relative to Merensky significant.
this volume). The Platreef horizon located reef. The PGE vary considerably in size
in the Potgietersrus area of the Bushveld from 1 to 200 m in size. Braggite and Stratiform chromite deposits occur in the
complex is substantially different to the vysotskite are coarser-grained while the Bushveld complex (UG2 reef, the UG, LG
Merensky reef, but is considered to be Pt-Fe alloys tend to be finer grained. & MG series reefs), the Great Dyke, the
the local equivalent of the Merensky reef The amount of PGE in solid solution Stillwater Complex (lower chromitites),
(Hochreiter, et al., 1985). Typical grades with the base metal sulphides is and the Muskox intrusion (Northwest
of PGE for this type of deposit range variable with the amount of Pd present Territories).
from 3 to 20 g/t PGE. in pentlandite, varying from 0.04 to
1.5%. An average head grade for the The UG2 Chromite
The Merensky Reef mill would run at about 24 g/t PGE The reef consists of 60-90% chromite,
In this case the term reef refers to (Turk, 2001). The talc in the ore is yet 5-25% orthopyroxene and 5-15%
a pegmatoid zone that is, in general, another similarity between the J-M and plagioclase with trace amounts of base
bounded by two thin (2-3 mm) chromite Merensky reefs. metal sulphides. The primary sulphides
layers. Mill head grades typically vary are pentlandite, pyrrhotite, chalcopyrite
from about 4 to 8 g/t PGE + Au. It should The Lac des Iles Complex and pyrite. The sulphide grains occur
be noted that as the mineralogy of the The primary PGE in the Lac des Iles typically in the size range 1 to 30 m
Merensky reef may vary in terms of complex is Pd. Major opaque minerals and occur mostly in the chromite grain
PGE, Base Metal Sulphides (BMS) and include pentlandite, pyrite, chalcopyrite boundaries. This phenomenon assists
gangue mineral characteristics, the and pyrrhotite. The most abundant PGE in liberation of the BMS, as the ore will
following comments are generalisations. is vysotskite (reported to have close only need milling down to the natural
The PGE occur as discrete PGM associations with pentlandite). Other chromite grain size (typically about
(primarily braggite, cooperite, laurite, PGM present include the braggite 100 m) in order to expose the BMS
sperrylite, moncheite and Pt-Fe alloys series of minerals, kotulskite, as well surfaces. The BMS can then be liberated
intergrown with base metal sulphides as antimonides and sulphantimondes by detachment. The PGM are typically
see appendix 2 for formulae of PGM) (Watkinson et al., this volume). As with associated with the BMS and will have
and in solid solution with the Cu, Ni the Merensky reef, there is a fair amount a size ranging from 1 to 2 m, and rarely
and Fe sulphides. The principal opaque of variability in the relative abundance exceeding 20 m. The principal PGM in
sulphide minerals are pyrrhotite, of the PGE. Similar to the Merensky the UG2 reef include: malanite, laurite,
pentlandite and chalcopyrite, listed in and JM reef, the PGE also occur in cooperite, braggite, Pt-Fe alloy, sperrylite
order of decreasing abundance. Minor solid solution with the BMS, with the and vysotskite. The PGM may also
sulphides include cubanite, mackinawite pentlandite containing between 0.02 occur as single grains along chromite
and pyrite (Cabri, 1981b; Cawthorn et and 0.65% Pd. The presence of talc in grain boundaries or as inclusions within
al., this volume). Typically, the PGE will the ore is consistent with the Merensky chromite or other silicate gangue
occur as fine inclusions within the BMS type ore. The average mill head grade minerals (Cabri, 1981b; Merkle and
or as intergrowths between the BMS for 2000 was 4.5 g/t Pd (North American McKenzic, this volume).
and gangue contact surfaces, which aids Palladium Ltd., 2001).
liberation during the grinding process. In
general, the liberation size is fairly coarse
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 4

The Lower Chromitites, Stillwater In the majority of placer deposits, the Class II: Intrusive equivalents of flood
Complex grain size decreases with increasing basalt associated with intercontinental
Although mineralogical studies have distance from the primary source. This rifting. The most significant example
shown the presence of PGM and BMS is significant when using placer deposits of this ore type is the Norilsk deposit
within these rocks it is unlikely that they for exploration purposes and should also in Russia. The Duluth complex in
will ever be economically exploited. The be taken into account when selecting Minnesota is another example of this
and encased in chromite (Cabri, 1981b; processing equipment for the recovery class of ore.
Zientek, this volume) and olivine and thus of various size ranges of PGM. In black Class III: Magmatic activity
not amenable to recovery by flotation placer sands, a portion of the Pt values accompanying the early stages of
unless very fine grinding is employed to may report to a magnetic concentrate, formation of Precambrian greenstone
liberate these minerals. It is likely that as some Pt-Fe alloys are ferromagnetic. belts. This class can be subdivided into
the grinding costs associated with the The presence of other heavy minerals in two further classes. Examples of Class
process will make the economics of the large quantities together with PGM may III deposits include the Kola Peninsula,
project unfavourable. complicate recovery as these minerals Lyn Lake, and Thompson and the
will be recovered simultaneously Northern tip of the Ungava Peninsula in
Podiform chromite deposits are mined with the PGM, thus, diluting the final Canada.
primarily for their metallurgical grade concentrate. Class IV: Tholeiitic intrusions, generally
chromium content. These chromitites synchronous with orogenisis in
may be enriched in Os-Ir-Ru alloys. In the Dunite Pipes Phanerozoic orogenic belts.
future, recovery of PGE as a by-product Dunite pipes occur in the eastern and
may be considered. Literature suggests western sections of the Bushveld The PGE in the ore types mentioned
that the Chinese may have already complex. These pipes have had reported above occur as discreet PGM and in solid
investigated this possibility (Cabri, grades of up to 2000 g/t PGE in some solution with BMS, and to a lesser extent
and Laflamme, 1981; Zhou et al., this sections. (Wagner, 1929). (Cut-off grades with gangue minerals. PGE recovery is
volume). As such the Podiform chromite of 3 g/t PGE have been reported). The not the prime driving force behind the
deposits should be strictly classed with mineralogy of the pipes differs greatly flowsheet development and optimization.
the other miscellaneous deposits. from the Merensky and UG2 reefs in However, in recent years, a concerted
that the sulphides of the PGE are rare. effort has been made to study the mode
Placer Type Fifty percent of the PGM are present as of loss for the PGE and to attempt to
These deposits include alluvial, eluvial Pt-Fe alloys; a further 30% of the PGM recover more PGM into the Cu and Ni
and Alaskan-derived type deposits. are present as sperrylite and geversite. concentrates.
(Cabri, 1981b). These pipes were
The PGM for all Alaskan-type bedrock exploited in the early 1900s. The PGM MISCELLANEOUS ORES
deposits and their derived placers are were recovered using gravity recovery These are ores in which the PGE is
similar. The most common PGM are methods, with recoveries between 82% present either in solid solution with other
Pt-Fe alloys and Ir-Pt alloys (Ir, Pt) is and 86% (Wagner, 1929). minerals or as discreet PGM. The PGE
the next most common minerals. Less are considered accessory metals and
common PGM such as osmium (Os,Ir,) Ni-Cu DOMINANT ORES the deposits are not mined for the sake
and iridium (Ir,Os) are also present, as As mentioned above these are ores in of the PGE and in some cases the PGE
well as a considerable number of rare which the primary financial value is due are not recovered as a co-product. The
PGM (Johan, this volume; Weiser, this to the Ni and Cu values. The PGE are following is a list of ores and deposits
volume). recovered as co-products and play a where PGE are present as an accessory
lesser role in project economics. metal:
The alluvial and eluvial deposits are
typically derived from weathered The classification and mineralogy for Porphyry Copper Ores: PGE are
ultramafic rocks. The PGM typically occur these ores will not be discussed in recovered from Cu refineries in the
as Pt-rich alloys in the form of loose detail, as the mineralogy and metallurgy United States and Canada as a by-
grains or nuggets. The high specific of these ores are well known and well product.
gravity and resistance to weathering understood, and not subject to the Copper-Molybdenum Deposits:
result in the concentration of Pt-rich culture of secrecy that has built up in Deposits in Armenia have measured up
PGM grains in placers along with other the primary PGE production sector. to 0.08 g/t Pd and 0.018 g/t Pt.
minerals with high specific gravity. Placer Carbonatite: The Palabora carbonatite
mining is believed to have begun in The following four classes of Ni-Cu ores complex in South Africa produces Cu
Colombia in the 1700s. Production from account for 95% of known Ni-Cu ores. from a low-grade chalcopyrite-valleriite
placer deposits in Russia began in the ore. The cathode slimes contained
1800s. In some alluvial deposits, the Class I: Noritic rocks associated with an about 16200 g/t PGE in 1974 (Note: the
PGM grains penetrate the underlying astrobleme (meteoric impact). The only corrected figure is given in Cabri, 1989,
bedrock, enriching the surface layers. known example of this ore type is the p 246).
Sudbury ore. Black Shales: The base metal-bearing
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 5

black shales from the Zechstein basin recovery circuits, the pyrrhotite is (typically greater than 100 g/t PGE
(Poland) contain PGE values ranging actively rejected or efforts are made to total), MgO content (typically 15-20%
from 20 to 400 g/t. Some PGM have minimise its recovery. max) and Cr2O3 content (typically 0.4 to
been identified but it is believed that The risk of over-grinding: The wide 2.8 max).
the platinum forms organic compounds range of mineral densities present Low concentrations of valuable
with kerogen. within typical primary PGE ores (talc minerals lead to froth stability and
Hydrothermal and Supergene Copper ~ 2.7, Fe-Pt alloys ~ 17.0) presents mass pull problems (entrainment etc.)
Ores: Pt and Pd-rich samples have been challenges within with grinding and
identified from the New Rambler mine classification circuits akin to those TYPICAL FLOTATION FLOWSHEETS
in Wyoming. experienced by gold producers with This section presents a number of
Nickel-bearing Laterite Deposits: Ni gravity-recoverable gold in the circuit. flowsheets from various operations.
laterites are formed by the chemical As cyclones are often used in the The flowsheets have all been published
weathering of ultramafic and mafic classification process, minerals with previously. References have been
rocks. The PGE hosted in the original a high density tend to be returned to provided with each flowsheet to enable
rock are concentrated in the Ni laterite. the milling circuit and are thus prone the reader to obtain more detail on each,
Concentration ratios are reported to to over-grinding that can lead to losses as the information that can be conveyed
range from 0.7 to 7 times the values in in PGE recovery. The various PGE here is limited due to the scope and
the original host rock. An example of producers have addressed the problem length of this paper.
this type of deposit would be the Black of over-grinding in many different
Range Syerston Project in Central New ways. Solutions to the problem have It should be noted that the ore
South Wales, Australia. (Motteram, included the use of screens in the mineralogy will dictate the process
2000). classifying process instead of cyclones, route chosen. Though the flowsheets
the inclusion of flash flotation (or presented have many similarities,
It is important to note that the majority unit flotation on mill discharge) in the there are many subtle differences in
of current primary PGE production is grinding circuit to recover liberated each flowsheet that are the result of
derived from sulphide ores. or near liberated minerals from the subtle and obvious differences in ore
cyclone underflows and the inclusion mineralogy.
SECTION II: BENEFICIATION OF of gravity recovery in the milling circuit.
PGE ORES Some producers have gone to the It is stressed that the flowsheets
extreme of using Mill Float, Mill, Float presented are intended to show features
circuits (or MF2) described in more that are characteristic of different regions
OVERVIEW
detail below, to prevent over-grinding on ore types. No weighting has been
The typical commercial method used for
of ores. Over-grinding of the ore can given to the number of ounces of PGE
the recovery of PGE from primary ores
also increase the risk of activating each type of flowsheet produces.
(other than placer deposits) is flotation.
or sliming certain gangue minerals
The flotation stage in recovery of PGE
(such as talc and chromite) that cause The South African MF2 Flowsheet
is responsible for the biggest single loss
complications in the down stream The MF2 circuit derives its name from
of PGE along the process route. Thus, it
smelting of the concentrates. Some the terminology Mill, Float, Mill, Float,
is logical that the concentrators should
important Pt carriers, such as sperrylite, i.e. MFMF or MF2. Figure 2 depicts a
be the focus of extensive research and
tend to losses during over-grinding typical MF2 type flowsheet.
development to continually improve on
because of the minerals brittleness and
the process.
its different flotation response (Cabri, The principal behind the MF2 circuit is
1988). two-fold: first, to prevent over-grinding
Some differences between typical base
The recovery vs. grade issue: in of the sulphides, in particular pentlandite
metal flotation circuits and flotation
typical base metal flotation circuits, which is prone to sliming. Secondly, to
circuits designed to treat PGE ores are
a certain minimum valuable metal prevent over grinding of actively floating
listed below:
grade is targeted for the concentrate. gangue material such as talc.
In PGE flotation circuits, the circuits The MF2 flowsheet consists of a primary
Pyrrhotite recovery vs. pyrrhotite
are run to maximise PGE recovery milling stage followed by primary
rejection: Various electron microprobe
with little or no regard for parameters flotation. The primary rougher tails are
studies have shown that pyrrhotite and
such as combined Cu/Ni grade or total then re-ground and floated in a second
other BMS contains varying amounts
S grade. (Some PGE concentrates stage, i.e. milling a rougher tail prior
of PGE in solid solution (Cabri, 1992;
have combined Cu/Ni grades of less to scavenging. The primary rougher
Distler et al., 1999). In addition to the
that 4%.) Some PGE producers buy concentrate and the secondary rougher
PGE present in solid solution, there
base metal concentrates to blend concentrate (scavenger concentrate) are
can be discreet PGM locked within
with their PGE concentrates to render cleaned in separate cleaning circuits with
pyrrhotite. This association of PGE
them smeltable. Factors that can one to three stages of cleaning in each
and PGM with pyrrhotite highlight the
control concentrate quality (and hence circuit. The cleaning circuits generally
importance of recovering pyrrhotite in
recovery of PGE) include PGE grade operated as a counter-current cleaning
a PGE operation. Typically, in non-PGE
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 6

Primary Milling Primary Flotation Secondary Milling Secondary Flotation

Final Tail

Primary Cleaning (1 to 3 Stages) Secondary Cleaning (1 to 3 Stages)

Final Concentrate

Figure 2. A Typical MF2 Flowsheet

stages. The cleaner tails from the scavenger flotation bank. The first cell in Primary grinding reduces the ore to
primary cleaner bank recycle to feed the the rougher bank produces final grade 45-50% -200 mesh. A centrifugal type
primary rougher, while the cleaner tails concentrate and this material can be concentrator is used in the milling circuit
from the secondary (scavenger) cleaner routed directly to the final concentrate. to recover a PGE concentrate. Up to
bank recycle to feed the secondary mill. The rougher concentrate is passed 40% of the PGE are recovered in the
directly to the cleaning circuit (no gravity concentration stage. A short
Variations in the flowsheets are regrinding) that consists of three column rougher flotation stage is utilised to
numerous and could include: cells operating in series. The stage remove liberated sulphides and PGM.
The first rougher cells concentrate recovery for each column is reported This rougher concentrate is routed
bypassing the cleaner circuit to report to be as low as 30%. The cleaner (final) directly to the final concentrate. The ore
directly to final concentrate concentrate is sent to a concentrate is then scavenged, and the scavenger
Gravity concentration of rougher thickener and dispatched to the smelter concentrate is cleaned once and
concentrate to recover liberated PGM complex in slurry form. The cleaner tail is reground prior to re-cleaning. The first
that will bypass the smelter and report recycled back to the head of the rougher and second cleaner tails are scavenged
directly to the precious metal refinery circuit. The scavenger concentrate can in separate circuits. The first cleaner
Flash or unit flotation incorporated into be routed to the head of the rougher scavenger concentrate is recycled to
the primary milling circuit bank or to the cleaner circuit. No the rougher tail, prior to scavenging. The
grinding is performed on the scavenger second cleaner scavenger concentrate
The Northam Flowsheet, South Africa concentrate. Figure 3 presents a is recycled to feed the first cleaner. The
The Northam Merensky concentrator schematic of the Northam flowsheet. Norilsk metallurgical group is currently
was designed to treat 270 t/h of run-of- (Snodgrass et al, 1994) presented a investigating the application of flash
mine (ROM) ore. A semi-autogenous detailed description of the Northam mill flotation (for disseminated ore) and
grinding (SAG) mill operating in open and process development. expects that this technology will find
circuit provides primary grinding. A ball a commercial application at Norilsk
mill operating in closed circuit provides The Norilsk Flowsheet (Alekseeva et al). Figure 4 presents a
secondary grinding. Flash flotation is Details on the concentrators at Norilsk schematic of the Norilsk flowsheet for
carried out on the cyclone underflow. are difficult to come by in Western disseminated ores. Please note the
The flash flotation cell recovers over literature. The following is a short flowsheet reported by (Kozyrez et al,.
60% of the PGE in the final concentrate. description of a flowsheet used in one this volume).
The cyclone overflow is conditioned of Norilsk concentrators to process a
prior to flotation. The primary flotation disseminated ore from the Norilsk-1
is undertaken in a single rougher/ Deposit.
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 7

The Stillwater Flowsheet


A detailed summary of operations at the
Stillwater Nye concentrator is described SAG Mill
in a paper presented by (Turk, 2001). Flash Float
Ball Mill

The ROM ore is milled in two stages,


utilising a primary SAG mill and
secondary ball mill. A flash flotation cell
(treating the ball mill cyclone underflow)
produces final grade concentrate. The Rougher Flotation Scavenger Flotation
target primary grind size is 145 m.
Primary flotation is undertaken in three Final Tail
stages: rougher flotation, middling
flotation and scavenger flotation. Final Concentrate
There is a tertiary milling stage (using
a verti mill) between the rougher and
middling flotation circuits. The middling
flotation concentrate is recycled back
to the head of the rougher circuit while
the scavenger flotation concentrate is
recycled to feed the middling flotation
circuit. Cleaning is achieved in three
stages operating in a counter-current
configuration. The concentrate from the
first stage of the first cleaner bypasses
Figure 3. The Norilsk Flowsheet
the second stage of cleaning and feeds
the third cleaners (two column cells
Flotation Feed 45-50% -200 Mesh
operating in series). The tailings from the
first part of the first cleaner are reground
prior to further cleaning. The cleaner
Scavenger Tails
circuit tails recycle to feed the rougher Rougher Scavenger

flotation circuit. Figure 5 presents a


schematic of the Stillwater flowsheet.
1st Cleaner 1st Cleaner Scavenger

The plant is reported to have a PGE


recovery of 91% and is producing a
concentrate containing 2000 g/t PGE.
The plant has a capacity of 3000 tonnes
ROM per day (Dyas and Marcus, 1998).
Regrind Mill (80-85% -325 Mesh)

The Lac des Iles Flowsheet 2nd Cleaner 2nd Cleaner Scavenger

Lac des Iles has recently commissioned


a new concentrating facility as part
of its expansion program to increase
mill throughput from 2,400 to 15,000 Final Concentrate
tonnes per day. The information for this Gravity Con From Mill
section was obtained from a fact sheet Circuit

issued at an open house to celebrate the Figure 4. The Stillwater Flowsheet

expansion (North American Palladium


Ltd., 2001). reground material is then cleaned in three stages, with the cleaners operating in a
counter-current configuration. The scavenger cleaner tail reports to the final tail. Figure
One SAG mill feeds two ball mills, at a 6 depicts a schematic of the Lac des Iles flowsheet.
rate of 15,000 tonnes per day. Two banks
of roughers and scavengers perform The expected feed grade to the plant is 2 g/t Pd and the targeted recovery is expected
the primary flotation. The rougher to increase from the mid-seventies to the low-eighties.
concentrate is reground and cleaned in a
single stage column. The rougher cleaner
tail joins the scavenger concentrate
and is reground in three Verti mills. The
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 8

REAGENTS FOR THE FLOTATION OF PGE Final Concentrate

ORES
In general, published literature on SAG Mill

reagent suites used in the PGE industry Flash Float


Ball Mill
has been sparse, However, there have
been a few papers that mention the
reagent suites used at the various
concentrators.

At Stillwater, the reagent suite consists


Tail
Rougher Flotation
of four chemicals. The collectors used
Verti Mill Middling Flotation
are potassium amyl xanthate, at a rate Scavenger Flotation

of 47 g/t and dithiophosphate (Cytec


Regrind Mill
3477), at a rate of 35 g/t. No frother is
used as the ore is naturally frothy and 1st Cleaner
3477 is a mildly frothing collector. The
original design did not use any 3477 but Final Concentrate

it was found to increase PGE recovery


2nd Cleaner 3rd Cleaner
by 2-4% (Hodges, Clifford, 1998).
The collectors are added to the flash
flotation cell, the rougher conditioner
Figure 5. The Lac des Iles Flowsheet
and the middlings feed (Turk, 2001).
Carboxylmethyl - cellulose (CMC) is used
200 g/t. Dithiophosphates are added Kozyev et al., this volume). The grade
for talc control and is added at a total
at rates varying from 10 g/t to 100 g/t. of the concentrate was 400 to 500 g/t
rate of 450 g/t (Hodges, Clifford, 1998).
The collectors are generally added to PGE. The equipment was tested on the
The CMC is added to the flash flotation
the rougher feed and scavenger feed. disseminated ore with a feed grade
cell, the rougher conditioner, the cleaner
CMC is used as a depressant and is of between 4.5 to 5.9 g/t Pt and Pd
conditioner, the second cleaner feed
generally added to the cleaning circuits. (Blagodatin et al, 2000).
and the middlings feed (Turk, 2001). It
Various frothers are used by the various
should be noted that the reagent dosage
producers. The Use of Dense Media Separation -
rates will in all likeliness change over
the years in response to varying ore Dense media separation is being used to
The Norilsk-1 mill (for disseminated ores) upgrade UG2 ores prior to milling. This
compositions. Sulphuric acid is used in
is reported to use isobutyl xanthate, enables miners to use wide reef mining
the rougher conditioner and middlings
sodium aerofloat (no designation given) techniques, substantially reducing mining
feed to control the pH to about 7.8. It
and organic oil-soluble calcium sulfonate costs. The chromite reef is removed from
has been noted that the recovery of PGE
in their reagent scheme for disseminated the lower density country rock. The most
drops off dramatically at the natural pH
ores. No information was published recent example of this type of installation
of the milled ore. CuSO4 (used as an
on reagent dosage rates or dosage is the new Kroondal mine. The
activator) which was part of the original
points (Alekseeva et al, 2000). Note technology is being considered for the
reagent suite but was removed as it did
that Kozyrev et al. (this volume) report Impala Winaarshoek project, scheduled
not contribute any apparent benefits in
a reagent scheme (used in the Norilsk- for construction in the first part of 2002
terms of recovery.
Talakh region) consisting of sodium (Lawrence, 2001).
butyl dithiophosphate; potassium butyl
The Lac des Iles reagent suite
xanthate for collectors, sodium dimethyl The Use of Large Tank Type Flotation
utilises potassium amyl xanthate and
dithiocarbonate as a depressant; NaHSO3 Cells
dithiophosphate (3477) as collectors,
as a modifier and CaO for pH control; More and more producers are using large
CMC as a depressant (for talc) and
pine oil and T-80 are used as frothers. tank type cells in new installations and
methyl isobutyl carbinol as a frother.
The author possesses no published plant upgrades. The motivation behind
information as to the dosages used. NEW TRENDS AND TECHNOLOGIES moving to the larger cells is largely
The circuit operates at natural pH (North The Use of Centrifugal Gravity driven by lower capital and operating
American Palladium Ltd., 2001). Concentrators costs associated with using large
South African producers are loath to Knelson and Falcon type centrifugal- equipment, rather than many smaller
publish any specific data on reagent type concentrators are being tested in units. Although subjective, it is possible
suits due to the historic culture of a number of applications in a number that simplifying the process and reducing
secrecy in the industry. Typically the of operations. The Norilsk mining the number of streams that an operator
collectors used are isobutyl xanthate company reports that up to 60% of the will need to monitor can improve the
and dithiophosphate. Xanthates are Pt and 13% of the Pd were recovered overall metallurgical performance
added at rates varying from 30 g/t to in the gravity concentrator (see also of a flowsheet. The rationale behind
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 9

this thinking is that the operators will Rougher Scavenger

dedicate more time to each circuit as


a whole and thus improve operational
response to the ore. Examples of large Tail
tank cell installations are the Impala
Merensky plant that has 18 x 130 m3
1st Cleaner
Ro Con Regrind
tank cells in the rougher circuit and the
new Lac des Iles concentrator that has
14 x 130 m3 tank cells in the scavenger
circuit.
Scav Con Regrind
Diagnostic Metallurgy and the Role of Rougher Con Cleaner
Process Mineralogy 2nd Cleaner

Detailed size-by-size analysis


encompassing both metal and
mineralogical balances of gangue,
sulphide and platinum group minerals is
helping the industry to build a detailed
3rd Cleaner
database of metal loss to tailings.
Although these investigations are time
consuming and costly, the benefits Con

far outweigh the costs. Technology Figure 6. PGE Feed Materials Discussed in this Review
and methods to improve analysis time
are actively being pursued. In South
PGE Feedstocks
Africa, the platinum industry is known
to use SEM-based imaging technology Primary Sources Secondary Sources
to significantly improve both final
recovery and final concentrate grade in
their concentrates. This technology is
also used in Canada for Ni-Cu ores, for
example, at Falconbridge. High Grade Low Grade Low Grade
High Grade
South African Inco Autocatalysts
Ultrafine grinding Stillwater Falconbridge Mint residues Electronic Scrap
Lac Des Iles Copper Smelters PGE Scrap
A feature commonly found in precious Norilsk (Noranda, Outokumpu,
metal flotation cleaner circuits is the Placer Concentrates Phelps Dodge)

presence of high circulating loads. The


reasons for running high circulating Figure 7. Standard Enrichment Process for High PGE Grade Concentrates

loads in PGE flotation circuits are varied.


In particular they include the presence
of complex middling particles and Table 1. Grades and Values of High Grade PGE and Typical Base Metal Concentrates

the presence of PGE-containing base


CONCENTRATE TYPE GRADE VALUE * (US$/TONNE)
metal sulphides such as pyrrhotite that
tend to exhibit slower flotation kinetics Copper 20-30% Cu 370-560
with extended residence times in a Zinc 50-60% Zn 460-555
flotation circuit. In the South African Lead 60-70% Pb 290-340
platinum industry there has always been
Nickel 5-12% Ni 330-790
a hesitancy to use re-grinding in the
PGE 0.02-0.2% PGE 2,330-23,330
cleaner circuits for a number of reasons
including the fear of sliming potentially Cu: 85 /lb: Zn: 42 /lb; Pb: 22 /lb; Ni: 3 $/lb; PGE: 350 $/oz
floatable particles (thus reducing * Assumed metal prices:
probability of recovery) and activating
gangue minerals such as talc. Recent
test work has focused on ultra fine
open-circuiting is that additional residence time is gained on the rougher bank by not
grinding of the cleaner tailings followed
re-circulating the cleaner tail. One South African PGE producer has reported (Steyn et
by flotation. It has been reported that
al, 2001; Curry, 2001) obtaining upgrade ratios of more than 60 when grinding cleaner
the newly liberated PGM and base metal
tails from a P50 of 18.6 m to a P50 of 7.1 m. Recoveries of PGE from the tails doubled.
sulphides exhibit high flotation recoveries
It should be noted that energy requirements for this size reduction are very high at
and that the cleaner tails can often be
approximately 60 kWh/t (Goodall et al., 2001).
open-circuited. A further advantage of
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 10

Circuit Simulation and Optimization A general observation to make before Pyrometallurgical Enrichment
The platinum producers in South Africa discussing the extractive metallurgy of Flotation concentrates generally need to
have been actively involved with the the PGE is the grade of the concentrates conform to many specifications to render
Amira P9 project to gain a deeper produced. Table 1 compares the grades them ideal for smelting. Parameters that
understanding of the fundamentals that and values of typical concentrates that tend to be important for concentrates
govern flotation performance. One part are processed to generate pure metals. generated from primary PGE producers
of the flotation research module in which include:
the Julius Kruttschnitt Mineral Research The values shown in Table 1 have two Sulphur content (if needed, sulphide
Centre (JKMRC) and the University implications on the extractive metallurgy rich ores are added to the smelting
of Cape Town (UCT) collaborate is of the PGE: the PGE concentrates are furnace to collect the PGE)
the Flotability Characterization Test too low-grade to be refined directly, and MgO content (typically 15-20%).
Rig (FCTR). The FCTR is essentially a will need to undergo an enrichment step Excess MgO is deleterious;
portable pilot plant with monitoring prior to refining. On the other hand, their Cr2O3 content (typically 0.4 - 2.8%).
equipment that is used to evaluate value is so high that the enrichment Excess Cr2O3 is deleterious; and
circuit changes, design concepts and step has to occur with minimum losses. Deleterious elements for smelting, e.g.
trial equipment. The test rig includes The enrichment step for primary and arsenic and bismuth
equipment needed to gather data secondary sources of PGE concentrates
required to model the system being (high and low grades) will be considered Limitations of the conventional smelting
tested. The model is validated against first, followed by the refining step and converting processes (Jones, 1999)
the pilot plant data obtained from the before discussing new developments. include:
FCTR. (JC World, 2001). As shown in Figure 7, both primary and SO2 emissions from the converting
secondary sources will be discussed. process are a continuing environmental
Froth Imaging concern. Intermittent operation of the
A number of groups are working on froth THE ENRICHMENT OF PGE converters makes handling of the off-
imaging or machine vision systems. CONCENTRATES gas in a sulphuric acid plant difficult.
The objectives are to capture data such The PGE concentrates processed to If ores with low sulphide contents
as the average grey level and froth recover their values can be divided into are processed, additional base metal
structure and to correlate the parameters primary (i.e. concentrates) or secondary concentrates need to be purchased to
with the metallurgical performance of the sources (recycled products like auto provide sufficient matte to allow for
flotation process. The effect of process catalysts, electronic scrap). effective coalescence of the droplets
parameters such as conditioning time, and collection of valuable metals.
and intensity as well as reagent additions Both primary and secondary sources To meet SO2 dispersion criteria in
on the froth structure has been studied can be subdivided into high grade and some parts of the world, smelters
and correlated to the froth structure and low grade concentrates; the high grade have to be shut down during certain
metallurgical performance. (Moolman et concentrates will be treated primarily for climactic periods (low wind velocities,
al., 1996) (Aldrich et al., 1997). their PGE content, while the PGE in the temperature inversions, etc).
low grade concentrates are recovered Discontinuous operation of converters
SECTION III: THE EXTRACTIVE as by-products of other metals, primarily is not conducive to stable plant
METALLURGY OF PLATINUM copper and nickel. operations.
GROUP METALS
Primary Sources The flotation concentrate composition
Typical PGE concentrates from primary must be suitable for smelting. Its rock
OVERVIEW
sources are, for example, the South mineral content should produce a fluid
The extractive metallurgy of the
African producers, Lac des Iles, Norilsk slag at the desired temperature. At the
platinum-group elements is fairly
(although primarily a nickel producer, same time, it must contain enough
complex and cannot possibly be covered
currently has more value from PGE, sulphides to form a reasonable quantity
in any detail in this overview. Therefore,
Likachev, 1999) and Stillwater for the of matte. To compensate for minor
most aspects of the PGE extractive
higher grades, or the Sudbury Basin problems with chemical composition,
metallurgy are covered, without in-
producers, (Falconbridge, Inco) for the various fluxes are added. Typically,
depth analysis, but rather by providing
lower grades. the main addition is burnt lime or
a detailed list of references to those
limestone but other materials such as
interested in further investigating any
High Grade Concentrates carbonaceous reductants, sulphides,
specific aspect.
Typical concentrate grades will range oxides or silicates are used as necessary.
from 200 g/t PGE to over 2,000g/t. Table 2 summarises typical concentrate
Moreover, this review intends to cover
The enrichment step is illustrated in a analysis from South African smelting
not only the processes industrially
simplified form in Figure 7. It is usually operations (Jones, 1999). Note the
applied but also other new technologies
a two-step process consisting in a higher Cr2O3 and PGE contents for the
developed for commercial application.
pyrometallurgical step followed by a
hydrometallurgical step.
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 11

Table 2. Typical South African Concentrate Analyses

Al2O3 CaO Cr2O3 Cu FeO MgO Ni S SiO2 PGE


% % % % % % % % % g/t
Amplats: Waterval 3.2 4.7 0.80 2.1 20 15 3.6 9 34 143
Amplats: Union 3.8 2.5 2.59 1.1 15 20 2.2 5 38 142
Impala 4.1 2.9 1.1 1.3 18 18 2.1 5.6 42 138
Lonmin: Merensky 1.8 2.8 0.4 2.0 23 18 3.0 9 41 130
Lonmin: UG2 blend 3.6 2.7 2.8 1.2 15 21 2.1 4.1 47 340
Northam 2.6 3.0 0.87 1.3 17 18 2.5 5.4 47 132

UG2 ores. It is also interesting to note two layers. The upper layer is a silicate/ treated. The power flux in the furnaces
the low Cu and Ni values in all of the oxide iron-rich slag, which is tapped off varies between 90 and 235 kW/m2. The
concentrates. and then either discarded or returned higher power fluxes are required for the
to the concentrator to recover any UG2 ores. The furnaces run with a slag
The concentrates are smelted in electric remaining PGE. The lower layer is an iron to matte production ratio of between 3.5-
furnaces. Large units with three to six sulphide-rich green matte which is sent 9.0. Tables 3 and 4 show typical furnace
electrodes in line are used for smelting. for converting. The sulphide minerals matte and furnace slag analysis from the
Smaller circular furnaces are used to form the matte, prills of molten matte various South African producers.
smelt unblended chromite concentrate. coalesces in the slag and then settle
Higher temperatures are required to melt out under the influence of gravity (slag The furnace matte is further processed
chromite concentrates (such as the UG2 S.G. ~ 2.7-3.3, matte S.G ~ 4.8-5.3). by converting. i.e. blowing of air into the
concentrates) owing to higher contents The rate of settling is controlled by the molten charge, over a period of a few
of chromium and magnesium oxides. viscosity of the slag which in turn can hours, to oxidise and remove the iron
More turbulent smelting conditions be controlled by the addition of fluxing and its associated sulphur. The oxidation
are also preferred to avoid build-up of agents such as limestone. The matte and reactions are sufficiently exothermic to
chrome spinel in the furnace hearth. slag are often tapped at opposite ends of maintain a temperature of about 1250C.
Typically, furnaces are run at about the furnace. The energy requirement for The temperature in the converter is
1350C, the UG2 furnaces can run smelting varies from 600-1000 kWh per controlled by adding cold feed or revert
at temperatures of up to 1600C. On tonne of concentrate depending on the material to the charge. Fluxing agents
melting, the concentrate separates into nature and grade of the material being (mainly silica sand) are added to form
an iron-rich slag that is skimmed off and
returned to the furnaces. The converter
Table 3. Typical South African Furnace Matte Analysis (Jones, 1999)
matte is granulated or slow-cooled.
Co % Cr % Cu % Fe % Ni % S% PGE g/t If the matte is slow cooled the PGE
Amplats: Waterval 0.5 0.5 9 41 17 27 640 concentrate on the grain boundaries
and tend to form ferromagnetic species
Amplats: Union 0.3 1.9 7 37 12 25 830
that can be recovered by magnetic
Impala 0.4 16 34 20 28 1050 separation. These ferromagnetic phases
Lonmin: Merensky 0.5 0.23 9.7 37 17 28 1000 are sent directly to the precious metal
Lonmin: UG2 blend 0.5 0.29 9.8 35 17 28 2500 refinery (Jones, 1999; Chamber of Mines
of South Africa, 2001). The converter
Northam 0.4 7.9 41 16 27 724
slag requires further treatment as the
vigorous turbulent conditions in the
converter cause entrainment of the
matte in the slag and oxidising conditions
Table 4. Typical South African Furnace Slag Analysis (Jones, 1999)
cause some base metals to dissolve in
Al2O3 % CaO % Cr2O3 % FeO % MgO % S% SiO2 % the slag in oxide form. The converter
slag is usually returned to the smelting
Amplats: Waterval 3.3 6.4 0.8 31 15 0.50 46
furnace, however, in some cases it
Amplats: Union 3.0 5.8 2.8 20 13 0.33 41 is treated in a separate slag-cleaning
Impala 6 8 1.2 21 18 0.25 47 furnace. Tables 5 and 6 show typical
Lonmin: Merensky 2.0 9.8 1.2 28 19 44 converter matte and converter slag
analysis from the various South African
Lonmin: UG2 blend 3.9 13 2.4 9.2 22 47
producers.
Northam 1.5 10 0.8 21 20 44
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 12

Recent descriptions of PGE smelters Table 5. Typical South African Converter Matte Analyses (Jones, 1999)
have been given (Cramer, 2001; Ndlovu,
Co % Cu % Fe % Ni % S% PGE g/t
2001; Kruger, 2001; Rule, 2001). As an
example of state-of-the-art smelter, Amplats: Waterval 0.5 26 2.9 47 21 2100
Anglo Platinum is presently installing a Impala 0.4 31 0.5 47 21 3430
new smelter complex in Pietersburg, Lonmin 0.6 29 1.4 48 20 6000
South Africa. The new furnace has
Northam 0.5 27 1.0 51 19 2570
been designed by Hatch and is a single,

Table 6. Typical South African Converter Slag Analysis (Jones, 1999)

Al2O3 CaO Co % Cr2O3 % Cu % FeO % MgO % Ni % S% SiO2 %


% %
Amplats: Waterval 0.7 0.4 0.45 0.4 1.17 63 1.1 2.25 2.4 27
Impala 1.8 0.3 0.43 1.4 1.06 64 0.71 1.90 1.0 27
Lonmin 0.7 0.5 0.39 1.4 0.94 65 0.78 1.43 1.7 28
Northam 1.3 0.7 0.4 0.36 1.37 64 0.82 2.18 27

six-in-line-electrode, furnace, of 68 MW Table 7. Chemical Analyses of Various Streams in the Stillwater Smelter (Hodges et al, 1991)
nominal operating power installed,
ELEMENTS SMELTER CONVERTER
capable of smelting 600,000 tonnes per
annum of concentrate. Latest advances CONC. GREEN MATTE SLAG WHITE MATTE SLAG
in furnace technology (waffle cooler) and PGEs (Pt + Pd) g/t 2,500 7,300 15 24,000 260
design will allow it to treat concentrates Cu % 3.6 11.8 0.09 30.5 1.8
with elevated levels of chromite (UG-2).
Ni % 5.2 17.7 0.12 44.0 2.8

Slag will be tapped continuously, Fe % 15.4 42.8 17.4 1.7 48.0


granulated and transported to a slag S% 13.7 27.4 0.5 21.8 2.0
dump. The green matte is tapped, cast, SiO2 % 31.9 - 45.0 - 18.0
cooled, crushed to minus 2 mm to suit
MgO % 12.3 - 14.8 - -
the new converter at Waterval. This new
CaO % 3.0 - 4.2 - -
converter (Wanblad, 2001), an Ausmelt
reactor, will produce white matte in two
stages. The converter slag containing too
high PGE values has to be recycled to Table 8. Typical Operating Temperatures for Smelting Low and High Chromite Concentrates
the process. Before, when treating low
TEMPERATURE (C)
chromite concentrates, the slag could
be recycled to the furnace; presently, Low Chromite Feed High Chromite Feed (2%
for high chromite concentrates, the slag (<0.5% Cr2O3) (Stillwater) Cr2O3)
is treated by milling and flotation, but a (Anglo Platinum Pietersburg)
slag cleaning furnace (a 30 MVA circular, Matte Tapping 1200-1250 1550
3-electrode furnace) is currently under Slag Tapping 1400-1450 1650
construction and will be operational in
Power Density 58 250
the fourth quarter of 2002.
(kW/m2)

Detailed metallurgical data are rarely


available. Table 7 presents industrial
results from the Stillwater Mining Co.s slow-cooled for a period of 3 days to facilitate the crystallisation of a metallic Ni-Cu-Fe
precious metals smelter (Hodges et al., alloy, representing about 15% wt% of the matte and containing about 99% of the PGE.
1991). See for example, some PGE (and Au) concentrations determined on individual minerals
from a similar assemblage to the phases found in matte (auge et al., 1999). This
Two additional items are to be pointed alloy is recovered by magnetic separation and the magnetic concentrate undergoes
out. The first point concerns the unique hydrometallurgical treatment whereby the base metals are dissolved leaving an
procedure practised at the Rustenburg enriched PGE concentrate for the precious metals refinery (PMR).
Waterval Smelter of Anglo Platinum,
(Hochreiter et al, 1985; Schouwstra, The second point concerns a clear trend for the South African smelters to treat high
2000) where the smelter green matte is chromite concentrates, reflecting the increased proportions of UG2 ores processed
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 13

in the Bushveld areas. Anglo Platinum


High Grade PGE Concentrate
projects that the chromite content of
their smelter feeds will increase from
1% Cr2O3 now to 3% Cr2O3 by 2020, if
SO2 Smelter Slag
the milling operations do not improve
Enrichment
their separation process (Rule, 2001).
If one recognizes the significant effect Step 1 = Green Matte
of chrome spinel on slag viscosities, Pyrometallurgical
it becomes very clear that smelters SO2 Converter Slag (Recycled)
handling UG2 concentrates have to
improve their process. In practice, this
White Matte
translates into operating furnaces at
higher temperatures. Table 8 illustrates Cu Solution
Enrichment Base Metal Refinery
the increased temperatures needed (BMR)
to efficiently treat high-chromite Step 2 = Ni Solution
concentrates. Hydrometallurgical
Power intensity of modern furnaces has PGE Concentrate

significantly increased over the last 35


years, which in turn puts much pressure PGE Refinery
on the type and quality of refractories
and on better means of removing
heat from the system (waffle cooler) Individual PGEs

(Wasmund, Francki, 2001). Figure 8. Simplified Flowsheet of Hartley Platinum Base Metals Refinery

Hydrometallurgical Enrichment - The


Base Metals Refinery Matte + PGEs

The hydrometallurgical enrichment step


consists in a reverse leaching operation Grind
whereby most of the accompanying Recycle

minerals (copper, nickel, cobalt and iron


sulphides) are dissolved to leave behind Atmospheric Cu
Reprecipitation
an upgraded PGE concentrate for the
PGE refinery.
L Ni, Co salt
To Ni, Co recovery products
The process to be used in the PGEs S

refineries has to meet the following two


objectives: Ni Atmospheric
dissolve as much as possible the metal Leach

sulphides without dissolving the PGE


and,
to effect as complete as possible a L
S
separation between the copper and
the nickel so that these two metals can
Ni Pressure
be recovered efficiently and generate L
S Fe2O3
marketable products. Leach

The same processes, as used in the L Pressure Fe Removal


S
nickel and copper-nickel refineries,
are being used for the PGE base
metal refineries (Kerfoot, 1986). For Spent Electrolyte
Cu Pressure Leach
the high-grade PGE refineries, there
are essentially two processes used
commercially, the Outokumpu process
and the Sherritt Gordon process. The L
To Cu recovery Cu product
S
chemistry underlying both processes is
the same.
PGE Concentrate

Figure 9: Simplified Flowsheet of Rustenburg Base Metals Refinery


SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 14

Table 9. PGE Matte Refineries in the Western World

PGE MATTE MATTE COMPOSITION BASE METAL LEACH PROCESS


REFINERY %Ni %Cu %Fe %S %PGE TYPE OXIDANT TEMP (C) PRESSURE
(kPa)
STILLWATER 42.5 28.1 3.1 22.6 2.1 S O2 Amb-135 Atm- 1000
HARTLEY* 44 33 1.0 21 0.15 O O2 85-150 Atm-
unknown
IMPALA 50 28 1.0 20 0.15-0.2 S Air 135 900
RUSTENBURG 47 22 3.0 21 0.15-0.2 S Air 135 1000
WESTERN 48 28 0.5-1 21 0.15-0.2 S O2 85-165 At-1100
PLATS
S = Sherritt Process; O = Outokumpu; Amb = ambient; Atm = atmospheric
*Not operating at present

The only PGE base metal refinery Ground Matte (+ PGEs )


using the Outokumpu process was
that of Hartley Platinum, in Zimbabwe.
That refinery is no longer in operation Atmospheric Leach

(Chadwick, 1996; Fugleberg, 1995).


A simplified process flowsheet of the
Hartley Platinum BMR is illustrated in S Pressure Leach
L
Figure 9.

S Pressure
All of the other PGM Base Metal L
Leach
refineries in the Western World use
the Sherritt Gordon process. A typical Purification Pb
example is the process used at the
S PGE
Rustenburg Base Metal Refiners, in L Conc
South Africa, as presented in Figure 10. Co Removal
Co

A simplification of the Sherritt process Solution


Se
Purification
is operated at the Stillwater refinery,
Ni EW Ni
as shown in Appendix 4, whereby no
Ni, Co salt
attempt is made to separate the nickel products
Cu EW
and the copper, and a bulk Ni-Cu solution
is shipped to an outside nickel refinery SO4 Removal Na2SO4
(Newman, Makwana, 1997; Kolstad, Cu
Newman, 1998).
Figure 10. Norilsk Complex - Existing Refining Process, Simplified
Detailed description of these processes
have been published (Brugman and
Kerfoot, 1986; Hofirek and Kerfoot,
1992l Hofirek and halton, 1990). Both
processes have the same rationale and
operate in several steps of increasingly
more aggressive conditions.
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 15

Ni - Cu - PGE ores
3Cu++ + SO4 + 4H2O Cu3(OH)4 SO4 +
4H+
Flotation
Tails
(hydrolysis)
(3)

Ni Conc These reactions provide a neutralised,


Cu Conc

SO2
iron and copper-free (pH 6.0, <10 mg/L
Electric Furnace
Smelting
Smelter SO2 Fe, Cu) suitable for the recovery of nickel
Slag metal and a cobalt product.
Converter
Slag
SO2
Slag Converting c. Iron removal: iron can be removed
Cu Blister
during the decopperization step
Ni Ref ining Cu Ref ining (atmospheric) as butlerite:

Fe+++ + SO4 + H2O Fe(OH)SO4 + H+


PGE Slimes PGE Slimes Cu
Ni (4)

Roaster Roaster or during a special high temperature


step, as hematite:

Ni Solution Leach Leach 2Fe+++ + 3SO4 + 3H2O Fe2O3 + 3


Cu Solution
H2SO4
(5)
EF Smelting Slag
The copper stream solution undergoes
a selenium-removal stage, that also
Electroref ining Solution (Ni) PGE Conc. 3 (Ir) removes any co-dissolved PGE, and
then is processed to copper metal in a
conventional electrowinning plant.
Anode Slimes Cu Sponge

Table 9 summarises production data for


Solution Leach Leach Solution Ag Conc.
the main high PGE matte refineries in the
Western world, collected from various
PGE Conc. 1 PGE Conc. 2 sources.
(Rh + Ru)
(Pt + Pd)
Norilsk
Figure 11. Norilsk Complex - New Base Metals Refining Process, Simplified
The Mining and metallurgical company,
Norilsk Nickel (MMC Norilsk Nickel), is
The initial stage operates under mild The major constituents of the matte are one of the largest producers of nickel and
conditions to leach some Ni and Co, a non-stoichiometric copper sulphide PGE in the world. Norilsk has operated
and uses fresh matte to remove Cu djurleite (Cu1.966S) and heazlewoodite a metallurgical complex to treat their
from the nickel sulphate solution; the (Ni3S2). ores for many years. The present process
central stage(s) operates under harsher is illustrated in Figure 11, as described
conditions and aims at dissolving all the The nickel stream is neutralised and recently (Ter-Oganesyants et al., 2000).
nickel and some copper from the matte; decopperized using matte. The reactions
the final stage aims at dissolving all the involved are: The PGE are recovered in the anodic
remaining copper and some iron from slimes from both the nickel and the
the matte. a. Neutralization: copper circuits. The slimes are roasted
Ni3S2 + O2 + 2H+ Ni++ + 2NiS + H2O and leached separately to recover the
The detailed chemistry of the base (1) nickel and the copper, respectively; the
metals refinery is outside the scope of leach residues are then combined in an
this review and has been described by b. Decopperization: electric furnace, wherefrom anodes are
several authors (Brugman, Kerfoot, 1986; 2Cu++ + Ni3S2 Cu2S + NiS + 2Ni++ electrorefined; the anode slimes are
Hofirek, Kerfoot, 1992; Hofirek, Halton, (metathesis reaction) leached in sulphuric acid to generate a
1990). It will only be discussed here (2) PGE concentrate #1 containing 60-
briefly. 65% (Pt + Pd); the copper spongy
and precipitate is also leached in sulphuric
acid to generate a PGE concentrate #2
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 16

containing 2.5-3.5% (Rh + Ru); finally , This concentrate will be autogeneously (chlorination). A new process to treat
the spent electrolyte, containing mainly smelted in Vanyukov furnaces to copper the placer platinum concentrate to
nickel sulphate, is treated to precipitate a blister at the Nadezhda smelter, and the maximise iridium and osmium recovery
PGE concentrate #3 assaying 10-20% Ir. precious metals recovered in the anode was developed by the Ekaterinburg
slimes during electrorefining of the Nonferrous Metal Processing Plant. It is
This process recovers higher than 99% copper blister. described in Figure 14.
of the major PGEs (Pt + Pd), but it has
a long processing cycle for the slimes A simplified flow diagram of the new Placer concentrates would be processed
(30 days), a large amount of material enrichment process is illustrated in in a series of steps:
in progress and is not very flexible for Figure 11. oxidizing roast plus smelting
processing other PGE feed materials. gases treated to recover osmium
Significant improvements will also be the metallic phase completely
A new process has been developed in- incorporated in the new PGE Refinery: dissolved
house by Norilsk Nickel to overcome the Pressure leaching will be used to gold recovery first, followed by
shortcomings of the present operation process the copper anode slimes (and successive recovery of Pt, Pd
and make use of the most modern the nickel anode slimes). iridium recovery and purification
technology Shestakova et al., 2000). Refinery wastes (rich in Rh), used (pyrometallurgical)
Several major modifications are being catalysts and gravity concentrates, will rhodium recovery and purification
incorporated at the flotation plant, the also be treated in separate lines. (molten salt)
smelter and the Base Metals Refinery. All resulting PGE concentrates will
be blended and smelted to matte in a
At the flotation plant, a bulk Cu-Ni Kaldo furnace.
concentrate will be produced, and the The resulting matte will be pressure
new mill is now being constructed by leached, and eventually will produce
Outokumpu Oy on behalf of Norilsk. a silver concentrate (AgCl), a PGE
concentrate #1 (Pt + Pd) as leach
At the smelter, a high copper converter residue, and a PGE concentrate #2, by
matte will be produced, with a copper-to- precipitation with thiourea and refining
nickel ratio of about 2:1; the matte will be to 35% (Rh + Ru + Ir).
granulated, wet-ground and then treated
in the new base metal refinery, that will With this process, the slimes processing
be using a new sulphuric acid leaching cycle will be reduced to four days. A
technology composed of: simplified flow diagram of the new PGE
an atmospheric decopperization refinery is presented in Figure 13.
process whereby matte is used to
decopperize the nickel anolyte Treatment of Placer Concentrates
atmospheric iron hydrolysis using nickel Russia is the leading producer of placer
or sodium carbonate (under oxidising platinum with 10t Pt produced in 1997,
conditions) representing half of its Pt production
an oxidising pressure leaching stage, from all sources (Valtukh et al., 1999).
followed by autoclave refining of the One of the major sources of iridium
copper concentrate in Russia is from placer platinum
maintaining the sulphur balance by concentrates, assaying 70-84% Pt,
treating a bleed of the nickel anolyte 1.7-9.2% Ir, 0.3-0.7% Pd, 0.4-0.6%
with sodium carbonate to produce Rh, 0.2-2.5% Os, 0.2-6% Au, 10-14%
nickel carbonate and a sodium sulphate Fe and other base metals (Cu, Ni).
effluent Other major sources are the iridium-
rich PGE concentrate from Norilsk,
This new process will result in a copper and recycled material (used crucibles,
concentrate containing all the copper (70- scrap) (Timofeyev et al., 2000). Placer
71% Cu grade), little iron (0.2-0.6% Fe), concentrates are presently treated at
little nickel (0.4-0.7% Ni), 26-28% S and the Krasnoyarsk Refinery, together
practically all of the PGE (plus gold). with Norilsk iridium by-product, using
only hydrometallurgical techniques
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 17

Ni - Cu - PGE ores

Flotation
Tails

Bulk Cu-Ni Conc

SO2
Smelter
Slag
SO2
Converter
Slag

Granulation
Grinding

Anolyte
Decopperization

S Pressure Oxidation
L Leaching

Atmospheric Fe
removal
Autoclave Ref ining

S
L Fe Cake
L
S

Co SX Co EW CuS + PGEs

Smelting
Co
Ni EW
(Vanyukov f urnace)

Cu Blister
Ni

Electroref ining
Figure 12. Norilsk Complex - New PGE Recovery
Process - Simplified
Anode Slimes (PGEs) Cu

Used Catalysts + Gravity


Ni Slimes Cu Slimes Ref inery Wastes Concentrate

Pressure Pressure Roaster Electric


Leach Leach Furnace

L Leach Matte Slag


S Ni Sol. L Sol.
S

L Sol.
Roaster S

Kaldo
Furnace

Matte

Pressure NaCl Thiourea


Leach

Ag Recovery PGE
L Barren
S Recovery

PGE Conc 1 AgCl PGE Conc 2


(Pt + Pd) (Rh, Ru, Ir)

Ag Ref inery

Ag

Figure 13. New Treatment Process for Placer Platinum


SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 18

Lower PGE Grade Sources Placer Platinum


There are other significant PGE NaOH

producers treating lower grade feedstock


Oxidising Roast and
materials such as, for example, Inco and Smelting Caustic Trap
Air Gases
Falconbridge. As opposed to the PGE (1000 - 1100C)
producers discussed previously, the PGE,
Slag
although significant contributors to the S
Pt, Pd, Rh, Ru, Au, Ir Ag, Ru
overall economics of these operations, L
Gravity
are nevertheless a by-product of nickel Concentration 10-25 g/L Os
Leach
(mostly), copper and cobalt. The process
Os Electrowinning
is, therefore, designed around the major
metal (nickel), while also maximising Tail

PGE recovery. Au Recovery Au Os oxides

Inco Reduction

The Inco process for the treatment Pt Recovery Pt


of its Sudbury ores has been well
Os
described (Wiseman et al., 1988; Tyroler
et al., 1988). Figure 15 summarises it Pd Recovery Pd
and indicates how the PGE high grade
concentrate(s) are produced.
Ir Recovery IrCl62-
Starting from a low PGE grade (1 g/t
PGE) in the mixed ore, Inco produces Calcination

refined nickel and copper and by-product Rh, Ru (+ Pt, Pd, Ir) Conc

precious metal concentrates, as anode Oxidation


slimes and carbonyl process residues. Molten Salt Melting
Electrolysis
The residue from the carbonyl process
assays 55-60% Cu, 6-10% Ni, 4-8% Co, Autoclave
Ir Treatment
4-9% Fe, 13-19% S, 600-900 g/t (Au + Further Ref ining
PGE) and 750 - 1350 g/t Ag. It is treated
Electron-beam
in a two-stage pressure leaching process vacuum Melting
to dissolve first the nickel and the
cobalt, and then the copper + selenium Ir
+ tellurium. PGE concentrate from the
Figure 14. Recovery of PGEs during Incos Treatment of Sudbury Ores
nickel circuit contains 60-80% (PGE +
Au), plus some silver and a variety of
The nickel and the cobalt are fully normally operate a precious metal plant
base metals such as tellurium, antimony,
recovered to pure metals from a chloride where anodic slimes are treated. Those
tin, lead, bismuth, copper, nickel and
system; the copper is roasted to slimes also contain significant amounts
iron. Concentrate from the copper circuit
sulphates and recovered conventionally of selenium and tellurium. The process
is largely palladium and platinum, with
from sulphate solutions. The PGE are used can vary from plant to plant. Three
some rhodium, and generally much
concentrated in the sulphuric acid leach examples will be briefly presented.
less base metals that the concentrate
residue. The residue is reduced to
from the nickel anode slimes. These
metal using hydrogen, and leached with Noranda CCR Refinery
concentrates are refined in the Incos
chlorine under controlled redox potential In 1998, Noranda CCR Division
Acton refinery in the UK, as will be
to minimise the dissolution of PGEs. commissioned a new anode slimes
discussed later.
The solid residue is the primary PGE treatment plant (Lessard, 1989; Bilodeau
concentrate; it is smelted to matte in an et al., 1987; Morrison, 1989; Morrison,
Falconbridge
electric furnace; the matte is granulated 1985). At that time, the plant process
Falconbridge in Sudbury treats ores
and leached with HCl/Cl2 to obtain the was as simply illustrated in Appendix 5.
similar to Incos but the approach to
final PGE product.
recover base metals and the PGE is
The process to recover gold from
completely different (Hougen et al.,
Copper Smelters the Moebius cell mud had remained
1975, Stensholt et al., 1988; Stensholt
Most copper concentrates contain largely unchanged since the 1930s.
et al., 1986, Stensholt et al., 2001). The
small, but not insignificant, quantities Disadvantages of this process were
Falconbridge process to recover PGE
of PGE. These eventually find their way, the large (30%) circulating load of Pd
from its ores is presented in a simplified
together with gold and silver, into the through the acid leach of gold mud from
form in Figure 16.
copper refinery anodic slimes. Most the Moebius cell, and significant gold
large copper refineries, therefore, in-process inventory.
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 19

Ni-Cu-PGE ores

Flotation Tails

SO2 Smelter Slag

Matte

Matte Separation by Flotation &


Magnetic Separation

Ni Matte Metallics
Cu2S Matte

Impure NiO Ni Ref inery (carbonyl


Roasting process)

NiO Ni
PGE
Cu Blister
Ni-Cu - PGE Ores

Flotation
Electroref inery Tails

Conc.

PGE Ref inery (Acton)


PGE Cu SO2 Smelter Slag

(Anode Slimes)
Figure 15. Falconbridge Chlorine Process to Recover Ni, Cu, Co and PGEs
Matte

A new process, developed at the Noranda Research Centre, has been installed to Shipped to Kristiansand, Norway
overcome these problems. A simplified process flowsheet of the new installation is
illustrated in Figure 17. Cl2 Ni-Co Leaching

The incoming gold mud typically assays 45% Au, 35% Ag, 14.2% Pd, 1.5% Cu and
0.5% Pt. The new process generates 99.99% Au, a 90% Ag cement for recycling to L To Ni, Co recovery
S
the Dore furnace, and a Pd/Pt concentrate assaying 90.8% Pd, 3.2% Pt, 2% Cu, 1.35%
Pb and 0.66% Se. In 1988, the silver refinery produced 801 tonnes of silver bullion,
26.6 tonnes of gold and 3.85 tonnes of Pd/Pt concentrate. Roasting

The Outokumpu Pori Refinery


H2SO4 Cu Leaching
The process used at Pori (Hyvrinen et al., 1984) is summarised in Appendix 6.

The electrolyte slimes undergo a series of stages: L To Cu recovery


S
decopperizing by oxidation leach, followed by filtration
nickel removal by pressure leaching at 160C
PGE Conc.
selenium removal from the slimes, followed by Dore smelting of the resulting slimes,
electrolytic silver refining in a Moebius cell Figure 16. New Hydrometallurgical Process to
Treat CCR Anode Slimes - (Simplified)
gold mud is further purified (H2SO4 leach) then dissolved in Aqua Regia
gold is recovered from solution by reduction (Na2SO3)
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 20

PGMs are cemented with iron to


Gold + PGE Mud
produce a 45% Pt, 45% Pd sponge.

In 1983, Outokumpu Pori refinery HCl


Leach
produced 38 tonnes of silver, 1.1 tonnes H2O2
of gold, and 2000 kg of Pt/Pd sponge
(45% Pt, 45% Pd).
S AgCl To Ag recovery
L
Phelps Dodge El Paso Refinery
The new refinery recently commissioned
to treat Phelps Dodges anodic slimes 1st Stage Au Precip.
SO2 Au
has been described in detail (Hoffmann,
Wesstrom, 1994). The process is
illustrated in a simplified form in Figure
18. SO2 2nd Stage Au Precip.

This is a very elegant process based on


an early separation of the silver (the main
constituent) from the rest of the precious S
L
metals, and gold solvent extraction.

The silver leaching step is based on the Na-Formate


Pd/Pt Precipitation
metathesis reaction: (pH=4)
NaOH
Ag2SO4 + Ca(NO3)2 2AgNO3 + CaSO4
(6) L Effluent Treatment
S
The calcium nitrate is produced by
reacting hydrated lime to consume nitric
Pt/Pd Conc.
acid generated at the anode, as per the
reaction: Figure 17. Simplified Process Flowsheet for Phelps Dodge Slimes Refinery

2HNO3 + Ca(OH)2 Ca(NO3)2 + 2H2O


(7) In 2000, 460,000 oz. of Pt and 230,000 Because of their high value (at 1000
oz of Pd were recovered, mostly in North g/t PGE, assuming an average price of
Very pure products are achieved using America, from recycled auto catalysts US $350/oz, a metric tonne of catalyst
this new process, 99.95% and 99.995% (8.5% and 2.9%, respectively, of the is worth US $11,550), the retreatment
for silver and gold, respectively. After total supply). of used catalysts has attracted much
2 years of operation, Phelps Dodge attention. In 1988, several processes
refinery was producing 3.1 M Tr. oz Ag, Auto catalysts are generally available had been identified to recover the PGEs
86.000 Tr. oz Au, 2,000 Tr. oz Pd and 200 in one of two forms, pellets or from auto-catalysts (Hoffmann, 1988;
Tr. oz Pt. monolith (honeycomb). The pellets Mishra, 1988). These were:
substrate (spheres or extrudes) is complete dissolution of the substrate
Secondary Sources: High Grade 100% -alumina; monolithic catalysts in sulphuric acid to obtain a high-grade
Recycled Products - Auto Catalysts employ a gel or wash coat of -alumina PGE residue for further treatment
High Grade Products on top of the honeycomb structure; dissolution of the -alumina substrate
Auto Catalysts the latter is composed of cordierite followed by HCl/Cl2 dissolution of the
Automobile catalytic converters (2MeO.2Al2O3.5SiO2, where Me is either PGEs away from the inert cordierite
(catalysts) are used to convert Fe or Mg). The catalyst itself could be structure
pollutants in automobile exhaust into two-way (Pt + Pd) or three-way (Pt + Pd dry chlorination
water vapour, carbon dioxide and + Rh). plasma fusion
nitrogen. Considering the size of the copper collection in dedicated smelters
automobile market and the emission Table 10 illustrates the composition of copper smelters
regulations, this represents a major new typical autocatalysts (Ferron et al., 2001,
sourceof the PGE, and recycling used Tucson). Sample A is a virgin monolithic The processes most likely to succeed
auto catalysts is becoming a significant catalyst, while Samples B and C are are the treatment of autocatalysts in
source of PGE. samples of used catalyst. conventional copper smelters, since no
incremental capital costs are incurred.
Recently published information has
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 21

described the operation of the new Table 10. Chemical Analysis of Typical Autocatalysts
Degussa dmC2 refinery in Hanau,
Germany (Hagelken, 2001). ELEMENTS VIRGIN USED
MONOLITHIC PELLETS MONOLITHIC
The process used for the treatment of SiO2 (%) 40.9 0.1 35.3
autocatalysts is illustrated in Figure 19.
Al2O3 43.7 91.1 40.3
MgO 10.8 0.1 9.8
The reduction furnace slag contains 10-
50 g/t PGE and is recycled to the copper Fe2O3 1.0 0.8 1.4
smelter. The Cu metal from the furnace P2O5 0.04 0.48 0.61
contains 10-15% PGE, and contains also MnO 0.02 1.23 2.09
iron and nickel.
Pb (g/t) <50 1500 550

High Grade Products - Mint Residue Pt (g/t) 623 322 1071


Residues from national mints do contain Pd (g/t) 431 134 -
significant PGE. Such an example is Rh (g/t) - - 45
given by a Brazilian mint residue assaying
13.6% Cu, 2.2% Fe, 1.6% Pb, 8.3%
S, 35.6% Pd, 0.9% Pt and 0.1% Au.
The process developed by the Centre Anodic Slimes

for Mineral Technology (CETEM) and


industrially applied is illustrated in Figure O2 Cu Pressure Leaching

20 (Sobral, Granato, 1992).


L
Cu, Te
The process used includes: S

dilute H2SO4 leaching to remove Cu, Fe


concentrated HNO3 leach to dissolve Sulphation Roasting
Se Ca(OH)2
H2SO4 (600C)
Pd (but not Pt, Au)
base metals precipitation (NH4OH)
yellow salt precipitation Fe3+ Ag Leach + Purif y
reduction with hydrazine to produce the
Pd powder
L Ag EW
S Ag
The purity of the palladium so produced
exceeds 99.95%.
HCl/Cl2 Au + PGE Leach

Recovery of Iridium from Zircon


Crucibles S Residue (To Smelter)
The refining of PGE is mostly based on L

the formation of chloro-complexes, but


Raf f inate Treatment
other chemistries are also available such DBC Au SX
as phosphates or fluorides (Patrushev,
1998; Izatt et al., 1987). It is known that Te reduction Hydrazine
iridium metal can be oxidised to form Oxalic Au Reduction

soluble fluorocomplexes, as per the


L
overall reaction (Mitkin, 2000): S
Melting
Ef f luent Treatment
Ir + 2BrF3 IrF5 + BrF + Br (8) Te + PGEs

Au
This property can be used to recover Split Recycled to Cu
pressure leach
iridium from ceramic zirconium (Y Al2O3
stabilized) blocks serving to produce Bleed

iridium crucibles, as indicated in


Appendix 7. PGE Concentrate

(Classical Precipitation)

In the process suggested, the iridium- Figure 18. Degussa dmC2 Process to Recover PGEs from Autocatalysts
contaminated zirconium block (0.8-1.2%
Ir) was oxidized to iridium (V) using
halogen fluoride (KBrF); after separation
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 22

THE REFINING OF PGE CONCENTRATES


Auto catalysts,
The final refining step consists in
Al2O3 chemical catalysts, transforming the high-grade PGE
ref ractories f rom glass industry concentrate (30-60% PGE) into high
purity (>99%) individual elements (Pt,
Pd, Ir, Os, Ru, Rh), as well as recovering
the gold and silver usually accompanying
the PGE.
Grind

Several papers describing the chemistry


and principles underlying the refining of
the PGE have been published (Edwards,
Cu Electric Arc Furnace Slag 1976; Demopoulos, 1989; Foo, 1982).
Cu Smelter
The success of the refining step is
based on manipulating, both from a
thermodynamic and kinetic point of view,
Cu (+ PGE) the complex aqueous chloride chemistry
of the PGE. Table 11 presents a list of
the most common chloro-complexes of
the precious metals, for each of their
Cu Leach oxidation states.
Cu

The relative abundance and stabilities


of these complexes depend on several
factors of which the most important are
PGE Conc.
the redox potential and the concentration
of chloride ion.
Figure 19. Brazilian Mint Process Flowsheet to Recovery Pd

Classical Refining
The methods developed many years
of the iridium fluoride formed (IrF5) The treatment of copper scrap consisted
ago to extract, separate and refine the
from the zirconium block, the solution of:
various platinum group metals are based
was treated with HCl to form the K2IrCl6 copper smelting and converting
on analytical chemistry principles. The
hexachloroiridate (IV). copper electrorefining
classical process circuit was initially
anode slimes purification by H2SO4
developed to treat electrolytic slimes;
Using this process, iridium recovery from leach (to remove Cu + Ni)
it is rather complex and is, in practice,
the zirconium block was 98-99%. Dore smelting and silver electrorefining
based on aqua regia solubilization
in a Thum cell
followed by successive steps of salt
Low-Grade Products: The Recycling of gold mud leaching with Aqua Regia
precipitation and redissolution, followed
Electronic Scrap gold reduction with SO2
by thermal reduction to metal.
Electronic scrap is normally recycled selective precipitation of red and yellow
to copper smelters, and therefore its salts
A few of the key properties
precious metals content is eventually
(thermodynamic or kinetic) commonly
recovered within the Cu refinery anodic When the amounts of PGE (Ir, Ru, Rh)
used to separate the various precious
slimes (Beke, 2001). were such that they would become
metals are presented below:
insoluble in the anodes, they were cast
AgCl is insoluble
There are plants, however, primarily and treated batchwise in a separate
AuCl4 is easily reduced to Au (fast
dedicated to the treatment of electronic circuit; the silver was recycled to the
kinetics and large thermodynamic
scrap. One such plant was the US main circuit, and the sludge was boiled
driving force).
Metals Refining Company (Amax) plant in aqua regia to solubilise Au, Pt, and
PtCl2--6 is very stable versus hydration,
in Carteret, New Jersey (Fruh, 1986; Pd. The residue containing Ir, Ru and Rh
unless Pt(II) is present
Manzone, Opie, 1977). About two-thirds was melted with Pb; the Pb-Rh alloy was
PdCl2--4 is the most labile of all PGE
of the 210,000 T/y copper produced leached with nitric acid to dissolve the
chloro-complexes, readily undergoing
by USMR originated from scrap. The Pb, and the crude rhodium purified. The
ligand exchange reaction of the type:
process can be described as illustrated in (Ir+Ru) rich nitric acid leach residue was
PdXn + L Pd Xn-1 L + X, where X =
Figure 21. fused with sodium peroxide to leach the
complexing radical and L= Ligand
Ru, while the residue was chlorinated
RhCl2--6 is the least stable of all PGE
and purified via the classical route to lr
chloro-complexes, easily undergoing
powder (Hoffmann, pers. Comm.).
hydration both from kinetic and
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 23

thermodynamic points of view.


PGE Residue
Ammonia readily forms insoluble
salts or compounds with various PGE
chloro-complexes, such as (NH4)2PtCl6, Base Metals Leach
H2SO4
Pd(NH3)2Cl2, (NH4)2IrCl6; this property
is commonly used to separate the
different platinum-group metals.
RuO4 and OsO4 (oxidation states + 8) L
S Cu, Fe
are stable and can be separated from
the other PGEs by distillation of their
tetroxides.
HNO3 Pd Leach

The classical refining process used for


many decades by Inco at their Acton
refinery in the UK is illustrated in Figure S Residue (Pt, Au)
L
22 and Figure 23. Details have been
published elsewhere (Demopoulos,
1989).
NH4OH Purif ication
In a very simplified form, the classical
process previously used at Acton can be
described as:
S Residue (Fe, Zn, Cu, Pb)
Aqua Regia dissolution of Au, Pt, Pd L
gold recovery from solution by
reduction
Yellow Salt
precipitation of (NH4)2 PtCl6 and HCl Precipitation
purification to Pt metal
precipitation of Pd(NH3)2Cl2 and Pd(NH3)2Cl2
purification to Pd metal Hydrazine N2H4
lead smelting of Aqua Regia residue Pd Reduction
NaOH
nitric leaching of silver, lead
bisulphate fusion of nitric leach residue
to solubilize and recover Rh Melting
peroxide fusion of residue to solubilize
Os, Ru, followed by precipitation of
RuO2 with ethanol and purification to
Os, Ru metals Pd
purification of residue to Ir metal Figure 20. Recovery of PGE from Electronic Scrap at USMR Carteret Plant

The process described in Figure 22 and


Figure 23 has been used for decades and Table 11. Most Common Chlorocomplexes of the Precious Metals

is still in use, partly or totally, in various


PRECIOUS METAL OXIDATION STATE MAJOR CHLOROCOMPLEXES
locations. It is rather complicated,
however; it gives a poor first time yield Silver I AgCl, AgCl2-
of refined metals and requires lengthy Gold III AuCl4-
refining times (up to 6 months for Platinum II PtCl42-
rhodium). It also results in significant IV
inventory or in-process of PGE, affecting PtCl62-
the overall economics of PGE refining Palladium II PdCl42-
because of the high cash value of the IV
metals that are held up. PdCl62-
Iridium III IrCl63-
Modern PGE Refining IV
Because of the factors described above, IrCl62-
the industry was forced to introduce Rhodium III RhCl63-
new separation technologies, namely Ruthenium III RuCl62-
solvent extraction (Barnes, Edwards,
Osmium III OsCl63-
1982; Anon, 1979; Rimmer, 1989; IV
Cleare et al., 1979; Cleare et al., 1981; OsCl62-
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 24

Edwards, 1977; Demopoulos, 1986; Scrap


Reavill, Charlesworth, 1990). Due to the Coke
selectivity and efficiency of the solvent
extraction process, several refineries Cupola Furnace Air + O2
have opted for a total leach approach (Shaf t) Slag (1-2% Cu)
followed by a sequential metal with the
aid of solvent extraction. Slag
Black Cu (80% Cu) Electric Furnace
There are three mechanisms by which Final Slag
solvent extraction of a metal species
can occur (compound formation, Air
Converter Fe-Cu (40-70% Cu)
ion-pair formation and solvation). All
SiO2
three mechanisms are encountered in
PGE solvent extraction, with ion-pair
formation by far the most important. Blister Copper
(98% Cu)

Table 12 from (Demoppoulous, 1989)


summarises data for the commercial Anode Furnace
application of solvent extraction for the
refining of precious metals.
Electroref ining Cu
Detailed information about the modern
refining schemes used at three of the
Anode Slimes
worlds largest PGE refineries (Inco,
MRR, Lonrho) has been published
(Demopoulos, 1989). More recent H2SO4 Cu-Ni Leaching
(220C) Cu,Ni Solution
information is lacking, and so is
information on the Krasnoyarsk refinery
in Russia, where most of Russia PGE are HNO3 Thumb Cells
Parting AgNO3
refined.

Au mud
The process used at Acton by Inco is Residue Ag
presented in a simplified form in Figure
23 (Barnes, Edwards, 1982): gold solvent PM Leaching
Aqua Regia AgCl Dore Furnace
extraction was introduced first in 1971
and, following its successful application,
work was undertaken to investigate the SO2 Au Reduction Au (Electroref ining)
applicability of SX to the separation of NH4Cl
the other precious metals in solution.
Selective
Zn Cementation Precipitation Ru,Rh,Ir
Refining of Iridium
During the treatment of placer-type PGE Cement
concentrate, iridium is recovered as an Pt(NH4)2Cl6 Pd(NH3)2Cl2
impure product ((NH4)2IrCl6) assaying
(Yellow Salt) (Red Salt)
31.33% Ir, 5.02% Pd, 1.44% Rh, 0.45%
Figure 21. Classical Refining Process for Au, Pt, Pd - Inco Acton Refinery
Pt. Classical methods will produce
high-purity iridium (for example by
precipitating the other PGEs ([Pd, Rh,
Pt] using H2S) but require complicated
equipment and iridium hold-up in
intermediate products is large. Another
approach, based on electrochemical
techniques, has been proposed to
refine iridium (Ermakov et al., 2000). The
process is presented in Appendix 8.
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 25

NEW TRENDS DEVELOPING


PM Concentrates
Smelting and Base Metals Refinery
Smelting of High Chromite Concentrates
Pretreatment (Roasting,
(UG2) Base Metals leach)
In the South African Bushveld, significant
PGE reserves lay within the high-
chromite UG2 reef. With the standard Aqua Regia Leach
smelting process, there is a limit on
the Cr2O3 content of the concentrate to
smelt, and this translates into a loss of S
L Residues (Ag, Ru, Rh, Ir)
PGE recovery during flotation, to meet
the specifications.
Au, Pt, Pd

Reductant (SO2, FeSO4) Gold Precipitation See Figure - 23


While efforts are underway to improve
PGE flotation recovery while achieving
the chromite specification, modifications Au (impure)
are also brought to the smelting process L
S
to allow higher chromite feeds. Some
of these modifications are already being Melting
Pt Precipitation NH4Cl
implemented, as described earlier
(Jones, 1999; Cramer, 2001).
Electroref ining
L
Higher temperature smelting to S

maintain slag viscosity to an acceptable


Au (Pure) Ignition
level, even at higher chromite content
NH3, Pd Precipitation
of the feeds. HCl
Slag cleaning to retreat the high Pt (impure)
chromite slag in a separate vessel so (NH3)2PdCl2
that most Cr2O3 is not returned to the NaBrO3
Releach, Purif ication
Aqua Regia, NaCl
smelter. NaOH
Purif ication
Mintek ConRoast process. Mintek has
NH4Cl HCl Pt Precipitation
recently developed and patented a
new smelting process that will allow HCOOH Ignition
treatment of high chromite feeds Ignition
(Jones, 2001). The new process is
Pd (Pure)
shown in its simplified form in Figure
Pt (Pure)
25.
Figure 22. Classical Refining Process for Ag, Ir, Os, Ru, Rh - Inco Acton Refinery

Several advantages are cited for this


process:
All the SO2 is captured during the dead
roasting operation.
The reductive smelting is not sensitive
to the Cr2O3 content of the feed.
Iron is a excellent collector for PGE.
A new leach process has also been
developed to recover PGE, Ni and Cu
from the Fe-PGE alloy.
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 26

Table 12. Commercial Solvent Extraction Systems for the Refining of Precious Metals (Demopoulos, 1989)

SOLVENT EXTRACTANTS METALS EXTRACTED INDUSTRIAL USERS COMMENTS


(a) Compound Formation
1. Alkyl sulphides (R2S) Pd(III) Inco
Lonrho (?) Slow kinetics
High metal loading
2. Phosphine sulphide (TIBPS) Pd(II) ? Pt/Pd separation based on
differential kinetics
3. Hydroxyoximes Pd(II) MRR Slow kinetics-low loading Use of
accelerator
(b) Ion-pair formation
1. Amines (Secondary; tertiary) Pd(II), Pt(IV), Ir(IV)
MRR (Pt;Ir)
PGP (?) Selective stripping difficult
Metal lock-up
2. Ammonium salts Pd(II), Pt(IV), Ir(IV), Rh(III) ? Very difficult stripping
3. Tri butyl phosphate (TBP) Pd(II),Pt(IV),
Ir(IV) Inco(Pt)
Lonrho (Ir)
Degussa (Pd,Pt,Ir) Acid conc. and redox
adjustment needed
(c) Solvation
1. Ketones (MIBK) Au(III) MRR Reduction to metal with Fe -
Impure product
2. Ethers (DBC) Au(III) Inco Reduction to metal with oxalic
acid-very pure product

Base Metals Refinery (BMR) The original second stage pressure Direct Leaching of PGE Ores/
The original BMR at Lonrho Platinum leach suffered from poor temperature Concentrates
in Marikana, South Africa has been control and excessive acidity, resulting Primary Sources
described in the literature. Recent in excessive PGE dissolution in the The present-day technology to treat high-
operating and flowsheet changes led to autoclave. The autoclave was re-designed grade PGE concentrates (smelting to
significant improvements (Steenkamp, to retain adequate control of sulphuric matte, Base Metals Refinery) performs
Dunn, 1999). acid concentration and retention time well and is well established. There are a
while maintaining temperature control few situations, however, where it is not
In the original process, the converter through the addition of cooling coils. suitable:
matte was poured into moulds and The concentrate is too low grade or
allowed to cool down before being The effect of these changes on the contains too many deleterious minerals
crushed. During this slow cooling, quality of the PGE concentrate is for the smelter (i.e. Cr2O3, MgO, As,
some sulphides oxidised to magnetite illustrated in Table 13. etc).
(FeO.Fe2O3) and trevorite (NiO.Fe2O3). The mine is remote and transportation
These ferrites did not leach in the BMR The modifications doubled the grade costs to a centralised smelter would be
leaching steps and reported to the PGE of the PGE concentrate and increased prohibitive.
concentrate, diluting it. In the modified the amount of PGE, mostly rhodium, Smelter contracts are not favourable to
process, the converter slag is water dissolved in the PGE refinery. small operators.
granulated to reduce ferrite formation
during cooling.
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 27

Aqua Regia Residue (Ag, Ir, Rh, Ru, Os) partial oxidizing roast of the concentrate
(From Figure 22) pressure leaching (HCl/HNO3) of calcine
filtration - washing
PbCO3 Smelting
activated C recovery of gold + PGE
PbSO4

HNO3 Nitric Parting AgNO3, Pb(NO3)2 Under those conditions, recoveries were
Ag (Pure)
95-98% Au, 94-95% Pt, 87-91% Pd, 78-
Aqua Regia Leach Residual (Au, Pt, Pd) 96% Cu, 82-92% Ni.

High Temperature Cyanidation Process


NaHSO4 Fusion (500C)
for the Coronation Hill Ore
The Coronation Hill (Australia) deposit
H2SO4 Rh Leach contains 3.5 M tonnes of ore assaying
5.1 g/t Au, 0.2 g/t Pt and 0.56 g/t Pd.
S
Since the ore could not be upgraded
L
Rh2(SO4)3 by flotation nor gravity, a cyanidation
NaOH
Peroxide Fusion Na2NO2 process was developed by CSIRO.
Precipitation
HCl
(500C)
NaOH Several options were examined, with the
Re-leach best results obtained using the process
NaNO2 illustrated in Figure 28 (Bruckard et al.,
Precipitation S IrO2
L
NH4Cl 1992).
Ethanol
(NH4)3[Rh(NO2)6] Ru Precipitation Aqua Regia Leach
NH4Cl The process eventually recommended
HCl
Re-leach included:
(NH4)2[IrCl6]
Precipitation S
NH4Cl L grinding - amalgamation
(NH4)2S
RuO2
HNO3 Purification high temperature (100-125C)
(NH4)3[RhCl6] NH4Cl cyanidation, followed by (Au + Pt) CIP
Purification
Purification
HCOOH (NH4)2[IrCl6]
Reductive Fusion
H2 (1000C) Na2[OsO2 (OH)4]6
H2 (NH4)3RuCl6 Reductive
H2 Table 13. Effect of Process Modifications on PGE
Fusion (1000C)
Reductive Concentrate Grade and Solubility
Rh (Pure) Reductive Fusion
(1000C)
Fusion (1000C) Ir (impure)
PGE % Dissolution in
Os (Pure) Ru (Pure) Conc. the Refinery
Figure 23. Modern Refining Process Scheme (Simplified) at Inco, Acton (UK) Grade PGE Pt Rh
(%)
Original 30 97 99.0 90.0
Because of these potential issues, much with air circuit
effort has been devoted to develop Leaching: 70C, 2 hours, 100 g/L H2SO4,
Modified 60 99 99.7 99.0
alternative process routes. Since 10 g/L NaBr (>800 mV ORP using Br2
circuit
hydrometallurgical plants are best suited (Geobrom 3400) as oxidant)
for small operations, this is the direction 24-40% solids
usually taken by the organisations
searching for alternative processes. A Under those conditions, recoveries were
few of these emerging new technologies 90% Au, 85% Pt and 70% Rh.
will be described in the following pages.
The North American Palladium Process
The BHP TML Process This process was developed at Lakefield
This process was developed to recover Research in the early 1990s (McDoulett,
PGE from the oxidised portion of Reschke, 1994) for the treatment of the
the Hartley deposit in Zimbabwe Lac des Isles PGE concentrate assaying
(Duyvesteyn et al., 1994). 4-6 g/t Au, 4-6 g/t Pt, 50-80 g/t Pd, 2.5-
3.0% Cu, 1.8 - 2.5% Ni, 12-12.5% Fe and
A simplified flow chart diagram of the 6-8% S.
TML process is presented in Figure 26.
The patented process is illustrated in
The following were the recommended Figure 27.
process parameters:
Roasting: 300-700C, 60-90 minutes, The process consisted of:
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 28

PM Concentrates
PGEs are then recovered from solution
using NaSH, while Cu, Ni, and Co are
recovered using conventional techniques.
HCl/Cl2, Leach 1
The process flowsheet for the NorthMet
concentrate is presented in Figure 29.
Results of a 10-day integrated mini-pilot
S Ag, Pb plant are summarised in Table 14.
L Pb, Ag Leach

The process has also been applied


Fusion successfully to numerous other PGE/
Na2O2
Cu-Ni concentrates, as well as to Cu-Au
(500-600C)
concentrates, Cu-Ni-PGE matte and Pt-
HCl/Cl2, Leach 2
laterites (Ferron et al., 2000a; Ferron et
al., 2000b; Ferron, Fleming, 2001).

S Residues (SiO2, AgCl,) Recycled Products: Auto Catalysts


L
USBM Process
Au + PGE + Base Metals In the early 1990s, the USBM developed
NaOH
Ru + Os Distillation Gas a process capable of recovering PGE
NaBrO3 RuO4, OsO4 from autocatalysts (Atkinson et al., 1992;
Kuczynski et al., 1992). A simplified
Separation, Refining flow diagram of the USBM process is
Base Metals S
L presented in Figure 30.

Os Ru More than 95% of the PGE were


MIBK Au SX Reduction, recovered in two successive leaches of
Au
Au
Refining the virgin monolithic catalysts, and more
than 90% from used pellet catalysts.
Pd SX Pd Reduction, Recovery dropped to 85-90% PGE on
DOS Pd
Refining used monolithic catalyst after three
successive leaches.
Pt SX Reduction,
TBP Pt Pt
Refining
South Dakota School of Mines Process
Chemical or SX Separation Reduction, Researchers at the South Dakota School
Rh Rh of Mines have been working for years
Refining
on developing processes to recover PGE
Ir Reduction, Ir from various products (including auto
Refining catalysts) using ammonia and/or halogen
salts, or halogen salts and sulphuric acids
Figure 24. Mintek ConRoast Process to Treat High Cr2O3 - PGE concentrates
and/or ammonium salts as key solvents
(Han, Meng, 1996).
High Chromite PGE Concentrate Under those conditions, extractions were
>95% Au, 90% Pd and 80% Pt. At 200C,with 87 psi oxygen over-
4.2.1.4. pressure and using sulphuric acid,
Dead Roasting SO2 H2SO4 ammonium iodide and ammonium
The PLATSOL Process bromide, 98% of the Pt, 92% of the Pd
The PLATSOL process was developed and 97% of the Rh were extracted in
Reductive Smelting Slag (+ Cr2O3) at SGS in the late 1990s by International one hour.
PGE Technologies to treat PolyMet
NorthMet (formerly Dunka Road) deposit McGill University Process
Fe - PGE Alloy within the Duluth Gabbro in Minnesota, The proce
USA (Fleming et al., 2000; Ferron et al., ss developed by McGill researchers
Ni Recovery 2000; Ferron et al., 2001). It is a high involved the percolation leaching of
Leach
temperature (>200C) pressure oxidation uncrushed pellets or 5-10 cm crushed
Cu Recovery
sulphate-based process with small monolithic catalyst, using an upward
PGE Conc.
additions of NaCl (5-20 g/L NaCl). Under flow of a 85-95C aluminium chloride/
those conditions, the base metals (Cu, hydrochloric acid/nitric acid leach mixture.
(To refinery)
Figure 25. Simplified TLM Process Diagram for Ni, Co) and the precious metals (Au, Pt, Ninety-eight percent of the PGEs were
the Hartley Oxide Ore
Pd) are dissolved in one single step. The recovered in 90 minutes leach time.
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 29

Hartley Oxide Ore PGE Conc

Roasting

Air Roasting
HCl
Pressure Leach O2
HNO3
(75C)
H2SO4
Leach Br2 (Geobrom 3400) S
L Residue
NaBr

Activated C Au,Pt,Pd
Au, Pt, Pd
S Residue
L
CaHS Cu Precip. CuS

Au + PGE Recovery (C or 1X) O2 Iron Precip. FeOOH

Figure 26. Process Flowsheet for the Treatment of the Lac des Iles PGE Concentrate
CaCO3O Ni Precip. NiCO3

Table 14. Pilot Plant Results - PLATSOL Treatment of the NorthMet Concentrate

H2SO4 HCl Regen. CaSO4


FEED STEADY-STATE
RESIDUE EXTRACTION % Bleed

Cu (%) 14.7 0.074 99.6 Figure 27. Process Flowsheet for the Treatment of
the Lac des Iles PGE Concentrate
Ni (%) 3.05 0.047 98.9
Co (%) 0.14 0.006 96.0
Ore
Fe (%) 32.9 44.07
Pd (g/t) 9.90 0.72 94.6
Pt (g/t) 2.22 0.12 96.0 Grinding + Gravity Coarse Gold
Au (g/t) 1.41 0.20 89.4

The aluminium oxide dissolved from acid consumption by recycling a High Temperature Cyanidation
the substrate was recovered as alumina large portion of the leach solution. (125C, 6 hours)
Al2O3 or alum Al2(SO4)3.nH2O (Letowski, The calcination step is not needed for
Distin, 1989). monolithic catalysts.

The Amax Process The Platinum Lake CRO - Redox Process CIP Tail
In 1981, Amax developed a process The process, developed at Ontario
to recover PGEs from spent catalysts Research Foundation (now Ortech) is
Au, Pt, Pd
(Bonucci, Parker, 1984). The process is illustrated in Figure 32 (Lakshmanan,
illustrated in Figure 31. Ryder, 1988; Lakshmanan et al., 1989). Figure 28. Process Flowsheet for the PLATSOL
Treatment of NorthMet Concentrate
The process recommended comprised:
calcination at 1500C The CRO process included:
PGE leaching (HCl/HNO3 ), followed by calcination at 100C for one hour
filtration/washing reduction pretreatment
lead precipitation from leach solution chloride leaching in the presence of a
using H2SO4 proprietary additive (Borohydride)
H2S precipitation of PGEs liquid/solid separation to remove lead
recycle of leach solution salts
treatment of a bleed to precipitate solvent extraction (Oxime - Kelex 100)
aluminium of both Pt, Pd followed by selective
stripping
The calcination step was required to precipitation (cementation) of Pt and Pd
transform the soluble -alumina into
insoluble -alumina, thereby decreasing
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 30

Ground Auto-catalyst
Bulk Concentrate

NaCN (1%) Autoclave Leach 160C,


1 hr
Regrind
NaCl L
S
Residue

Pressure Leach Thermal Decomposition


(275C)
(225C, 2 h, 100 psi O2)
L
S Barren (<0.2 mg/L CNT)

H2O Hot Filtration Tailings


PGE Conc (60-70% PGE)

PLS Figure 30. Flowsheet for the Treatment of Spent


Catalysts. The Amax Process
NaHS Precipitation
NaHS
metals compared to the major PGE (Pt,
Pd). A commercial process conditions
the Ir-Rh chloride solution by adjusting
S its chloride content and oxidising
PGE Concentrate
L the iridium to the Ir (IV) stage before
extracting it using a solvating extractant
(TBP or N-substituted monoamide).
Partial Neutralisation (pH The efficiency of the separation is
CaCO3 ~2) based on the fact that rhodium can
only form hexachlorocomplexes in
very concentrated chloride solutions;
in addition, the order of extraction of
S Gypsum Cake chlorocomplexes depends strongly on
L (discard) the charge of the complex, with doubly
charged anions (IrCl-26) being extracted
more strongly than triply charged anions
Cu SX/EW (RhCl36).
Cu
Recent work has indicated that the
Ni/Co solvent extraction of rhodium from
Raf f inate Bleed chloride solutions is greatly improved
Recovery
(75%) (25%) with the addition of SnCl2 (Mhaske et al.,
Figure 29. Simplified Flow Chart Diagram of the USBM Process
2001; Shafiqul et al., 1997).

Leaching recoveries were >93% for Pt refineries has resulted in a flurry of


and >98% for Pd. research into finding alternative reagents
for the selective extraction of the PGE.
The PLATSOL Process Table 16 presents a non-exhaustive list
The PLATSOL process has been of extractants tested for the recovery of
described earlier. It was also tested PGE.
on various auto catalysts (Ferron et al.,
2001a). The most elusive area appears still to
be the development of a commercial
Good extractions are obtained as per SX process for the recovery of rhodium
results presented in Table 15. (Benguerel et al., 1996; Nicol, 2000).
Typically, the iridium and rhodium
Refining of PGE Concentrates are recovered after all the other PGE
Solvent Extraction have been recovered because of the
The success of solvent extraction as difficulties of the separation and the
applied in some of the largest PGE lower concentrations of these two
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 31

is then polished with SuperLig 133 to


Ground Spent Catalyst (Pellet)
produce a 99.95% minimum Rh purity.

In 1997, Impala installed a MRT system


Calcination (1500C) for the separation and purification of Pd
in their primary PGE refinery (Robinson,
1995; Van Tonder et al., 2001). The
HCl installed system is comprised of 16
Leaching columns each with 32 kg of SuperLig.
HNO3 The process is shown in Figure 33.
(105-110C)
Typical purities of 99.98-99.99% Pd are
achieved. With the introduction of the
S Residue (Al2O3)
L MRT system, overall Pd recoveries have
been improved while shortening the
overall process route.

H2SO4 Purification PbSO4 Resin TP-207 (Bayer). It is a selective


resin, normally sold as a sodium salt
of the iminodiacetic acid functional
group. The resin has been piloted by
H2S PGE Recovery PGE Sulphide Conc
Noranda to recover Pd from Moebius
cell electrolyte (Rosato, Shink, 1989).
During silver electrorefining, Pd and Cu
Lime Purification Al(OH)3 dissolve and accumulate in the nitrate
electrolyte, and a bleed is required to
control the build-up of these elements
and maintain silver purity. Starting
Barren
from electrolytes assaying 150-200
Figure 31. Platinum Lake Process Flowsheet g/L Ag, 100 mg/L Pd and 15-25 g/L Cu,
using the TP 207 resin, palladium was
reduced to less than 5 mg/L. Eluting
Ion Exchange Resins SuperLig reagents have been the loaded resin with 50-100 g/L HNO3
Several ion exchange resins have been developed for various duties. removed co-adsorbed copper; the Pd
developed and tested for application in was then stripped using 100-150 g/L
the PGE industry. Two commercial PGE operations are HCl.
known to have introduced MRT systems
Polyisothiourea (PITU) (Warshawsky, in their refinery.
1983). These chelating resins are not
selective; they serve to extract all PGE Tanaka Kikinzoku Kogyo (TKK) precious
selectively vs. the base metals. The metal refinery near Tokyo recovers
elutant is thiourea, and the PGE can rhodium from the refinery feedstream
then be separated by precipitation or containing PGE and base metals, using
solvent extraction. five columns in series of SuperLig 96.
Amborane Resins (Rohm, Haas) Starting from 17 g/L Rh, 98% of the Rh
(Demopoulos, 1989). They are mildly is recovered in one pass. The Rh eluate
reducing agents (amine-boranes),
reacting with the precious metals
Table 15. PLATSOL Results on Various Auto Catalysts
to produce boric acid and metallic
precious metal covering the polymer
ELEMENT VIRGIN USED
bead. It is unfortunately not selective
and it has to be burned to recover the (MONOLITHIC) (MONOLITHIC) (PELLET)
precious metals on it. g/t % Rec g/t Feed % Rec g/t Feed % Rec % Rec
SuperLig (IBC Advanced Technologies) Feed (1) (1) (2)
(Ruckman, 1989): These are molecular
Pt 663 97.1 998 84.9 335 72.1 93.7
recognition ligands (MRT) that are
Pd 470 98.6 - - 141 86.0 95.2
engineered in such a manner as to
allow only ions of the correct size Rh - - 44.7 66.1 - - -
to fit into their active sites. Different
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 32

Table 16. Some of the Chemistry Tested for PGE SX

EXTRACTANT APPLICATION REFERENCE


1. 8-Hydroxyquinoline derivative Pd(II) + Pt(IV), Demopoulos,1989
(8-HQ) Selective stripping Demopoulos, et al., 1989
- Kelex 100, LIX 26 Pd(II) + Pt(IV), Yan, et al., 1994
- TN 1911 Selective stripping
- Kelex 100 Rh

2. Pyridine Carboxylic Esters Pd(II) Burgess, et al., 1990


- Acorga CLX-50 Dalton, et al., 1993

3. Hydroxyoximes Pd(II) Jackson, 1992


- P50
4. Oxime Pd(II) Dimmit et al, 1989
- MOC-15 (Allied Signal)
5. Octylamine pyridine (OAP) Rh Petrukhin et al., 1980
6. Trioctylamine (TOA) All PGE selectively Kuzmichev, et al.
from base metals in
nitrite solution
7. Phenylbenzamidines Pd(II) Antico, et al, 1994
8. Benzoyl Thiourea Pd(II) Antico, et al, 1994

Spent Catalyst

Borohydride
Reductive Pre-
treatment (95C)

Chloride Leaching

(85C, emf >600 mV)

S Residue
L

Barren
Pt, Pd Solvent Extr. Barren

Selective Strip Pt

Bleed
Pd Strip Pt Strip
Figure 32. Platinum Lake Process Flowsheet
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 33

CLOSING COMMENTS

The preparation of a review to cover the beneficiation and extractive metallurgy of the
platinum group elements is not an easy task, for several reasons.

There are six elements in the group (usually plus gold), and are usually found
associated with each other. Their chemical properties are sufficiently close to make
their separation difficult.

Because of their high value, they are recovered from low-grade resources (a few grams
per tonne) and from a large variety of host minerals. Due to their low concentration
in the process feeds, fairly elaborate techniques have to be used to measure their
chemical and mineralogical properties.

Although the situation has significantly improved over the last few years, published
information is rather limited when compared to other metals. This is due to the
very competitive nature of that business segment on one hand, and to geopolitical
events on the other hand, that resulted in decades of complete blackout of technical
information from the former U.S.S.R., one of the very large PGE producers.

Because more than 90% of the world PGE originate from only two countries, there
was a temptation to concentrate only on the information released from Russia and
South Africa, and not paying enough attention to the wealth of good technical data
originating from other sources. The authors have attempted to incorporate in this
review the published information available to them from sources throughout the world,
irrespective of the size of the operation, even to include operations not longer in
existence.

ACKNOWLEDGEMENTS

The authors are grateful to the several reviewers who, with their corrections,
comments and suggestions, significantly contributed to improve the quality of this
review. Included were: James Hoffmann (J. Hoffmann and Associates), Prof. Tai Yen
(Queens University), Dee Bradshaw, Peter Gaylard and Martin Wright, (University of
Capetown), and Chris Fleming, (SGS).
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 34

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Geology, Geochemistry, Mineralogy and Mineral Beneficiation of Platinum-Group
Elements. Edited by L.J. Cabri. Canadian Institute of Mining, Metallurgy amd
Petroleum, this volume, p. 459-481.
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 39

APPENDICES
Appendix 1: Pt, Pd and Rh Supply Statistics for the year 2000 (J. Matthey, 2001)

ORIGIN Pt Pd Rh
000s oz. % Total 000s oz. % Total 000s oz. % Total
South Africa 3,920 72.5 1,960 24.7 434 58.8
Russia 1,100 20.3 5,200 65.7 280 38.0
North America 285 5.2 665 8.4 20 2.7
Others 105 2.0 95 1.2 3 0.4
Total 5,410 100 7,920 100 737 100
Major PGE Mining Companies
Anglo Platinum (Amplats) - South Africa
Norilsk Nickel - Russia (Primary and Secondary PGE producer)
Impala Platinum (Implats) - South Africa
Lonmin Platinum (Lonplats) - South Africa
Medium and Smaller-size PGE Mining Companies
North American Palladium Ltd. - Canada
Stillwater Mining Co. - USA
Aquarium Platinum (Kroondal) - South Africa
Northam Platinum (Gold Fields of South Africa) - South Africa
Southern Era (Messina) - South Africa
Koryakgeoldobycha - Russia
Mimosa - Zimbabwe
Major Secondary Producers
Falconbridge - Canada
Inco - Canada

Appendix 2: PGM Mentioned in this Text

MINERAL IDEAL FORMULA GENERAL FORMULA


Braggite (Pt, Pd)S (Pd, Pt)S (Pt, Pd, Ni)S
Cooperite PtS (Pt, Pd, Ni)S
Kotulskite PdTe Pd(Te,Sb,Bi)
Laurite RuS2 (Ru, Os, Ir)S2
Sperrylite PtAs2 (Pt, Rh)(As, Sb, S)2
Moncheite PtTe2 (Pt, Pd)(Te, Bi)2
Vysotskite PdS (Pd, Ni, Pt)S
Geversite PtSb2 Pt(Sb, As, Bi)2

Appendix 3: Equipment Specifications

Some Equipment specifications for the Northam Flowsheet


SAG Mill Diameter: 8.5 m (inside shell)
SAG Mill Length: 3.05 m (EGL)
SAG Installed Power: 4.4 MW (variable speed)
Ball Mill Diameter: 5.5 m (inside shell)
Ball Mill Length: 6.7 m (EGL)
Ball Mill Installed Power: 4.4 MW (variable speed)
Rougher Flotation Cells: 6 x 38 m3 Outokumpu cells
Scavenger Flotation Cells: 6 x 38 m3 Outokumpu cells
Cleaner Columns: 3 x 2.44 m diameter by 122.5 meter high

Some Equipment specifications for the Stillwater Flowsheet


SAG Mill Diameter: 1.83 m
SAG Mill Length: 5.5 m
SAG Installed Power: 800 Hp
Ball Mill Diameter: 4.0 m (70% critical speed)
Ball Mill Length: 6.1 m
Flash Flotation Cell: SK240
Rougher Flotation Cells: 4 Parallel banks of tank type cells
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 40

Tertiary Grinding: 1250 Hp Verti mill (target grind size 100 m)


Middling/Scav. Flotation: 4 Parallel banks of 5 cells each, total of 170 m3 capacity
First Cleaner: 1 x 10 m3 cleaner, 2 x 10 m3 cleaner scavs. (tank
type)
Second Cleaner: 2 x 5 m3 (tank type)
Third Cleaner: 2 x 0.9 m x 9.1 m Columns
Cleaner Regrind Mill: 1.5 m x 2.4 m Ball Mill

Some Equipment specifications for the Lac des Iles Flowsheet


SAG Mill Diameter: 30 ft
SAG Mill Length: 14 ft
SAG Installed Power: 8, 500 HP
Ball Mill Diameter: 20 ft
Ball Mill Length: 34 ft
Rougher Flotation Cells: 2 Parallel banks of 50 m3 tank type cells.
Scavenger Flotation: 2 Parallel banks of 7 cells each. 130 m3 capacity
per cell
First Cleaner: 9 x 30 m3 (tank type)
Second Cleaner: 8 x 5 m3
Third Cleaner: 2 x 4 ft x 36 ft Columns
Rougher Regrind Mill: 200 HP Verti mill
Scavenger Regrind Mill: 3 x 1,250 hp Verti mills

Appendix 4: Simplified Flowsheet of Stillwater Base Metals Refinery

Matte + PGE

Grind

Atmospheric Leach

L Shipment To Ni, Cu
S recovery plant

O2
Pressure Leach
H2 SO4

L
S

PGE Concentrate
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 41

Appendix 5: CCR Anode Slimes Treatment Plant in 1988

Anode Raw Slimes

O2 Cu Pressure Leach CuSO4 Solution, Te

O2 Se
TBRC Furnace
Flux Slag

Slag Dore Furnace Se

Anodes
Flotation

Moebius Cell Ag

Final Slag

Gold + PGE Mud

H2SO4 Ag Leach (300C) Ag2SO4 + Pd (To Dore)

Wohwill Cell Au

Na Formate Pd-Pt Precipitation Pd/Pt Conc.

Barren Appendix 6: Precious Metals Refining Process Used at Outokumpu Pori Refinery

Anode Slimes

Air Cu Leach (80C) L CuSO4 solution


S

H2SO4 Ni Leach (160C) L


S NiSO4 solution

SO2 Roaster Se

Borax Dore Furnace


Slag
Na2CO3 (1250C)

O2
Refining Pb, Cu, Te
Na2CO3

Dore Anodes

Gold Mud Moebius Cells Ag

H2SO4 Ag Leach Ag Solution

Aqua Regia Au Leach Residue (To Furnace)

Na2SO3 Au Reduction Au

Fe PGE Reduction Solution

PGE Sponge
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 42

Appendix 7: Fluoride Recovery of Iridium

Zircon-Ir Blocks
Air
F2
Fluorination (80- Annealing
KBrF4 200C) (2-4 hrs)

Zircon block (for


HCl Chlorination
reuse)

K2IrCl6

Appendix 8: Electrochemical Refining of Iridium Concentrates

Impure (NH4)2IrCl6

Reductive Leaching
Na2S2O3
(90C)

Purification

S
L Impurities

Electrowinning Cathode (Pt, Pd, Rh + 5% Ir)

Pure Ir Solution (30 g/L Ir)

HCl Precipitation Impure (NH4)2IrCl6

Calcination (1000C)
99.4% Ir

Appendix 9: Abbreviations used in the review

DBC - Dibutyl/carbitol
DOS - Di-n-octyl sulfide
TBP - Tributyl Phosphate
MRR - Matthey Rustenburg Refinery
MIBK - Methyl Isobutyl Ketone
SGS MINERALS SERVICES TECHNICAL BULLETIN 2002-03 43

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